Molecular sieve compositions, catalyst thereof, their making and use in conversion processes

ABSTRACT

The invention relates to a catalyst composition, a method of making the same and its use in the conversion of a feedstock, preferably an oxygenated feedstock, into one or more olefin(s), preferably ethylene and/or propylene The catalyst composition comprises a molecular sieve and at least one oxide of a metal from Group 4, optionally in combination with at least one metal from Groups 2 and 3, of the Periodic Table of Elements.

CROSS REFERENCE TO RELATED APPLICATIONs

[0001] The present application claims priority under 35 USC 120 fromU.S. Provisional Patent Application Serial No. 60/360,963 filed Feb. 28,2002 and from U.S. Provisional Patent Application Serial No. 60/366,012filed Mar. 20, 2002, and is related to U.S. Patent Application SerialNo. 60/374,697 (Attorney Docket 2002B057)filed concurrently herewith andU.S. patent application Ser. No. 10/215,511 (Attorney Docket 2002B 106)filed concurrently herewith, the entire contents of which applicationsare incorporated herein by reference.

FIELD

[0002] The present invention relates to molecular sieve compositions andcatalysts containing the same, to the synthesis of such compositions andcatalysts and to the use of such compositions and catalysts inconversion processes to produce olefin(s).

BACKGROUND

[0003] Olefins are traditionally produced from petroleum feedstocks bycatalytic or steam cracking processes. These cracking processes,especially steam cracking, produce light olefin(s), such as ethyleneand/or propylene, from a variety of hydrocarbon feedstocks. Ethylene andpropylene are important commodity petrochemicals useful in a variety ofprocesses for making plastics and other chemical compounds.

[0004] The petrochemical industry has known for some time thatoxygenates, especially alcohols, are convertible into light olefin(s).There are numerous technologies available for producing oxygenatesincluding fermentation or reaction of synthesis gas derived from naturalgas, petroleum liquids or carbonaceous materials including coal,recycled plastics, municipal waste or any other organic material.Generally, the production of synthesis gas involves a combustionreaction of natural gas, mostly methane, and an oxygen source intohydrogen, carbon monoxide and/or carbon dioxide. Other known syngasproduction processes include conventional steam reforming, autothermalreforming, or a combination thereof.

[0005] Methanol, the preferred alcohol for light olefin production, istypically synthesized from the catalytic reaction of hydrogen, carbonmonoxide and/or carbon dioxide in a methanol reactor in the presence ofa heterogeneous catalyst. For example, in one synthesis process methanolis produced using a copper/zinc oxide catalyst in a water-cooled tubularmethanol reactor. The preferred process for converting a feedstockcontaining methanol into one or more olefin(s), primarily ethyleneand/or propylene, involves contacting the feedstock with a molecularsieve catalyst composition.

[0006] Molecular sieves are porous solids having pores of differentsizes such as zeolites or zeolite-type molecular sieves, carbons andoxides. The most commercially useful molecular sieves for the petroleumand petrochemical industries are known as zeolites, for examplealuminosilicate molecular sieves. Zeolites in general have a one-, two-or three-dimensional crystalline pore structure having uniformly sizedpores of molecular dimensions that selectively adsorb molecules that canenter the pores, and exclude those molecules that are too large.

[0007] There are many different types of molecular sieve well known toconvert a feedstock, especially an oxygenate containing feedstock, intoone or more olefin(s). For example, U.S. Pat. No. 5,367,100 describesthe use of the zeolite, ZSM-5, to convert methanol into olefin(s); U.S.Pat. No. 4,062,905 discusses the conversion of methanol and otheroxygenates to ethylene and propylene using crystalline aluminosilicatezeolites, for example Zeolite T, ZK5, erionite and chabazite; U.S. Pat.No. 4,079,095 describes the use of ZSM-34 to convert methanol tohydrocarbon products such as ethylene and propylene; and U.S. Pat. No.4,310,440 describes producing light olefin(s) from an alcohol using acrystalline aluminophosphate, often designated AlPO₄.

[0008] Some of the most useful molecular sieves for converting methanolto olefin(s) are silicoaluminophosphate molecular sieves.Silicoaluminophosphate (SAPO) molecular sieves contain athree-dimensional microporous crystalline framework structure of [SiO₄],[AlO₄] and [PO₄] corner sharing tetrahedral units. SAPO synthesis isdescribed in U.S. Pat. No. 4,440,871, which is herein fully incorporatedby reference. SAPO molecular sieves are generally synthesized by thehydrothermal crystallization of a reaction mixture of silicon-,aluminum- and phosphorus-sources and at least one templating agent.Synthesis of a SAPO molecular sieve, its formulation into a SAPOcatalyst, and its use in converting a hydrocarbon feedstock intoolefin(s), particularly where the feedstock is methanol, are disclosedin U.S. Pat. Nos. 4,499,327, 4,677,242, 4,677,243, 4,873,390, 5,095,163,5,714,662 and 6,166,282, all of which are herein fully incorporated byreference.

[0009] Typically, molecular sieves are formed into molecular sievecatalyst compositions to improve their durability in commercialconversion processes. These molecular sieve catalyst compositions areformed by combining the molecular sieve and a matrix material usually inthe presence of a binder. The purpose of the binder is hold the matrixmaterial, often a clay, to the molecular sieve.

[0010] Although it is known to use binders and matrix materials to formmolecular sieve catalyst compositions useful in converting oxygenatesinto olefin(s), these binders and matrix materials typically only serveto provide desired physical characteristics to the catalyst composition,and have little to no effect on conversion and selectivity of themolecular sieve. It would therefore be desirable to have an improvedmolecular sieve catalyst composition having a better conversion rate,improved olefin selectivity and a longer lifetime.

[0011] U.S. Pat. No. 4,465,889 describes a catalyst compositioncomprising a silicalite molecular sieve impregnated with a thorium,zirconium, or titanium metal oxide for use in converting methanol,dimethyl ether, or a mixture thereof into a hydrocarbon product rich iniso-C₄ compounds.

[0012] U.S. Pat. No. 6,180,828 discusses the use of a modified molecularsieve to produce methylamines from methanol and ammonia, where forexample, a silicoaluminophosphate molecular sieve is combined with oneor more modifiers, such as a zirconium oxide, a titanium oxide, anyttrium oxide, montmorillonite or kaolinite.

[0013] U.S. Pat. No. 5,417,949 relates to a process for convertingnoxious nitrogen oxides in an oxygen containing effluent into nitrogenand water using a molecular sieve and a metal oxide binder, where thepreferred binder is titania and the molecular sieve is analuminosilicate.

[0014] EP-A-312981 discloses a process for cracking vanadium-containinghydrocarbon feed streams using a catalyst composition comprising aphysical mixture of a zeolite embedded in an inorganic refractory matrixmaterial and at least one oxide of beryllium, magnesium, calcium,strontium, barium or lanthanum, preferably magnesium oxide, on asilica-containing support material.

[0015] Kang and Inui, Effects of decrease in number of acid siteslocated on the external surface of Ni-SAPO-34 crystalline catalyst bythe mechanochemical method, Catalysis Letters 53, pages 171-176 (1998)disclose that the shape selectivity can be enhanced and the cokeformation mitigated in the conversion of methanol to ethylene overNi-SAPO-34 by milling the catalyst with MgO, CaO, BaO or Cs₂O onmicrospherical non-porous silica, with BaO being the most preferred.

[0016] International Publication No. WO 98/29370 discloses theconversion of oxygenates to olefins over a small pore non-zeoliticmolecular sieve containing a metal selected from the group consisting ofa lanthanide, an actinide, scandium, yttrium, a Group 4 metal, a Group 5metal or combinations thereof.

SUMMARY

[0017] In one aspect, the invention resides in a catalyst compositioncomprising a molecular sieve and at least one oxide of a metal selectedfrom Group 4 of the Periodic Table of Elements, wherein said metal oxidehas an uptake of carbon dioxide at 100° C. of at least 0.03, andtypically at least 0.035, mg/m² of the metal oxide.

[0018] The catalyst composition may also include at least one of abinder and a matrix material different from said metal oxide.

[0019] The catalyst composition may also include an oxide of a metalselected from Group 2 and Group 3 of the Periodic Table of Elements. Inone embodiment, the Group 4 metal oxide comprises zirconium oxide andthe Group 2 and/or Group 3 metal oxide comprises one or more oxidesselected from calcium oxide, barium oxide, lanthanum oxide, yttriumoxide and scandium oxide.

[0020] The molecular sieve conveniently comprises a framework includingat least two tetrahedral units selected from [SiO₄], [AlO₄] and [PO₄]units, such as a silicoaluminophosphate.

[0021] In another aspect, the invention resides in a molecular sievecatalyst composition comprising an active Group 4 metal oxide and aGroup 2 and/or a Group 3 metal oxide, a binder, a matrix material, and asilicoaluminophosphate molecular sieve.

[0022] In another aspect, the invention resides in a method for making acatalyst composition, the method comprising the step of physicallymixing first particles comprising a molecular sieve with secondparticles comprising a Group 4 metal oxide having an uptake of carbondioxide at 100° C. of at least 0.03 mg/m² of the metal oxide particles.

[0023] In one embodiment, the molecular sieve, a binder and a matrixmaterial are made into a formulated molecular sieve catalyst compositionthat is then contacted, mixed, combined, spray dried, or the like, withan active Group 4 metal oxide, such as an active zirconium metal oxideand/or an active hafnium metal oxide, optionally in the presence of aGroup 2 and/or a Group 3 metal oxide.

[0024] In another aspect, the invention resides in a method of making acatalyst composition, the method comprising:

[0025] (i) synthesizing a molecular sieve from a reaction mixturecomprising at least one templating agent and at least two of a siliconsource, a phosphorus source and an aluminum source; and

[0026] (ii) recovering the molecular sieve synthesized in step (i);

[0027] (iii) forming a hydrated precursor to a Group 4 metal oxide byprecipitation from a solution containing a source of Group 4 metal metalions;

[0028] (iv) recovering the hydrated precursor formed in step (iii);

[0029] (v) calcining the hydrated precursor recovered in step (iv) toform a calcined metal oxide that has an uptake of carbon dioxide at 100°C. of at least 0.03 mg/m² of the metal oxide; and

[0030] (vi) physically mixing the molecular sieve recovered in step (i)and the calcined metal oxide of step (v).

[0031] In yet another aspect, the invention is directed to a process forproducing olefin(s) by converting a feedstock, such as an oxygenate,conveniently an alcohol, for example methanol, in the presence of any ofthe above molecular sieve compositions and/or molecular sieve orformulated molecular sieve catalyst compositions.

[0032] In yet another aspect, the invention is directed to a process forconverting a feedstock into one or more olefin(s) in the presence of amolecular sieve catalyst composition comprising a molecular sieve, abinder, a matrix material and a mixture of metal oxides different fromthe binder and the matrix material.

[0033] In one embodiment, the catalyst composition has a LifetimeEnhancement Index (LEI) greater than 1, such as greater than 1.5. LEI isdefined herein as the ratio of the lifetime of the catalyst compositionto that of the same catalyst composition in the absence of an activemetal oxide.

DETAILED DESCRIPTION OF THE EMBODIMENTS Introduction

[0034] The invention is directed to a molecular sieve catalystcomposition and to its use in the conversion of hydrocarbon feedstocks,particularly oxygenated feedstocks, into olefin(s). It has been foundthat combining a molecular sieve with one or more active metal oxidesresults in a catalyst composition with an enhanced olefin yield and/or alonger lifetime when used in the conversion of feedstocks, such asoxygenates, more particularly methanol, into olefin(s). In addition, theresultant catalyst composition tends to be more propylene selective andto yield lower amounts of unwanted ethane and propane, together withother undesirable compounds, such as aldehydes and ketones, specificallyacetaldehyde.

[0035] The preferred active metal oxides are those having a Group 4metal (for example zirconium and hafnium) from the Periodic Table ofElements using the IUPAC format described in the CRC Handbook ofChemistry and Physics, 78th Edition, CRC Press, Boca Raton, Fla. (1997).In some cases, it is found that improved results are obtained when thecatalyst composition also contains at least one oxide of a metalselected from Group 2 and/or Group 3 of the Periodic Table of Elements.

Molecular Sieves

[0036] Molecular sieves have been classified by the Structure Commissionof the International Zeolite Association according to the rules of theIUPAC Commission on Zeolite Nomenclature. According to thisclassification, framework-type zeolite and zeolite-type molecularsieves, for which a structure has been established, are assigned a threeletter code and are described in the Atlas of Zeolite Framework Types,5th edition, Elsevier, London, England (2001), which is herein fullyincorporated by reference.

[0037] Crystalline molecular sieves all have a 3-dimensional,four-connected framework structure of corner-sharing [TO₄] tetrahedra,where T is any tetrahedrally coordinated cation. Molecular sieves aretypically described in terms of the size of the ring that defines apore, where the size is based on the number of T atoms in the ring.Other framework-type characteristics include the arrangement of ringsthat form a cage, and when present, the dimension of channels, and thespaces between the cages. See van Bekkum, et al., Introduction toZeolite Science and Practice, Second Completely Revised and ExpandedEdition, Volume 137, pages 1-67, Elsevier Science, B.V., Amsterdam,Netherlands (2001).

[0038] Non-limiting examples of molecular sieves are the small poremolecular sieves, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI,DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG,THO, and substituted forms thereof; the medium pore molecular sieves,AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON, and substituted formsthereof; and the large pore molecular sieves, EMT, FAU, and substitutedforms thereof. Other molecular sieves include ANA, BEA, CFI, CLO, DON,GIS, LTL, MER, MOR, MWW and SOD. Non-limiting examples of preferredmolecular sieves, particularly for converting an oxygenate containingfeedstock into olefin(s), include AEL, AFY, AEI, BEA, CHA, EDI, FAU,FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON. In onepreferred embodiment, the molecular sieve of the invention has an AEItopology or a CHA topology, or a combination thereof, most preferably aCHA topology.

[0039] The small, medium and large pore molecular sieves have from a4-ring to a 12-ring or greater framework-type. In a preferredembodiment, the zeolitic molecular sieves have 8-, 10- or 12-ringstructures and an average pore size in the range of from about 3 Å to 15Å. In a more preferred embodiment, the molecular sieves, preferablysilicoaluminophosphate molecular sieves, have 8-rings and an averagepore size less than about 5 Å, such as in the range of from 3 Å to about5 Å, for example from 3 Å to about 4.5 Å, and particularly from 3.5 Å toabout 4.2 Å.

[0040] Molecular sieves have a molecular framework of one, preferablytwo or more corner-sharing [TO₄] tetrahedral units, more preferably, twoor more [SiO₄], [AlO₄] and/or [PO₄] tetrahedral units, and mostpreferably [SiO₄], [AlO₄] and [PO₄] tetrahedral units. These silicon,aluminum, and phosphorus based molecular sieves and metal containingderivatives thereof have been described in detail in numerouspublications including for example, U.S. Pat. No. 4,567,029 (MeAPO whereMe is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871 (SAPO), EuropeanPatent Application EP-A-0 159 624 (ELAPSO where El is As, Be, B, Cr, Co,Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. Pat. No. 4,554,143 (FeAPO), U.S.Pat. Nos. 4,822,478, 4,683,217, 4,744,885 (FeAPSO), EP-A-0 158 975 andU.S. Pat. No. 4,935,216 (ZnAPSO, EP-A-0 161 489 (CoAPSO), EP-A-0 158 976(ELAPO, where EL is Co, Fe, Mg, Mn, Ti or Zn), U.S. Pat. No. 4,310,440(AlPO₄), EP-A-0 158 350 (SENAPSO), U.S. Pat. No. 4,973,460 (LiAPSO),U.S. Pat. No. 4,789,535 (LiAPO), U.S. Pat. No. 4,992,250 (GeAPSO), U.S.Pat. No. 4,888,167 (GeAPO), U.S. Pat. No. 5,057,295 (BAPSO), U.S. Pat.No. 4,738,837 (CrAPSO), U.S. Pat. Nos. 4,759,919, and 4,851,106 (CrAPO),U.S. Pat. Nos. 4,758,419, 4,882,038, 5,434,326 and 5,478,787 (MgAPSO),U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. No. 4,894,213 (AsAPSO), U.S.Pat. No. 4,913,888 (AsAPO), U.S. Pat. Nos. 4,686,092, 4,846,956 and4,793,833 (MnAPSO), U.S. Pat. Nos. 5,345,011 and 6,156,931 (MnAPO), U.S.Pat. No. 4,737,353 (BeAPSO), U.S. Pat. No. 4,940,570 (BeAPO), U.S. Pat.Nos. 4,801,309, 4,684,617 and 4,880,520 (TiAPSO), U.S. Pat. Nos.4,500,651, 4,551,236 and 4,605,492 (TiAPO), U.S. Pat. Nos. 4,824,554,4,744,970 (CoAPSO), U.S. Pat. No. 4,735,806 (GaAPSO) EP-A-0 293 937(QAPSO, where Q is framework oxide unit [QO₂]), as well as U.S. Pat.Nos. 4,567,029, 4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197,4,917,876, 4,952,384, 4,956,164, 4,956,165, 4,973,785, 5,241,093,5,493,066 and 5,675,050, all of which are herein fully incorporated byreference.

[0041] Other molecular sieves include those described in R. Szostak,Handbook of Molecular Sieves, Van Nostrand Reinhold, New York, N.Y.(1992), which is herein fully incorporated by reference.

[0042] The more preferred molecular sieves include aluminophosphate(AlPO) molecular sieves and silicoaluminophosphate (SAPO) molecularsieves and substituted, preferably metal substituted, AlPO and SAPOmolecular sieves. The most preferred molecular sieves are SAPO molecularsieves, and metal substituted SAPO molecular sieves. In an embodiment,the metal is an alkali metal of Group 1 of the Periodic Table ofElements, an alkaline earth metal of Group 2 of the Periodic Table ofElements, a rare earth metal of Group 3 of the Periodic Table ofElements, including the Lanthanides: lanthanum, cerium, praseodymium,neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium,erbium, thulium, ytterbium and lutetium; and scandium or yttrium, atransition metal of Groups 4 to 12 of the Periodic Table of Elements, ormixtures of any of these metal species. In one preferred embodiment, themetal is selected from the group consisting of Co, Cr, Cu, Fe, Ga, Ge,Mg, Mn, Ni, Sn, Ti, Zn and Zr, and mixtures thereof. In anotherpreferred embodiment, these metal atoms discussed above are insertedinto the framework of a molecular sieve through a tetrahedral unit, suchas [MeO₂], and carry a net charge depending on the valence state of themetal substituent. For example, in one embodiment, when the metalsubstituent has a valence state of +2, +3, +4, +5, or +6, the net chargeof the tetrahedral unit is between −2 and +2.

[0043] In one embodiment, the molecular sieve, as described in many ofthe U.S. patents mentioned above, is represented by the empiricalformula, on an anhydrous basis:

mR:(M_(x)Al_(y)P_(z))O₂

[0044] wherein R represents at least one templating agent, preferably anorganic templating agent; m is the number of moles of R per mole of(M_(x)Al_(y)P_(z))O₂ and has a value from 0 to 1, preferably 0 to 0.5,and most preferably from 0 to 0.3; x, y, and z represent the molefraction of Al, P and M as tetrahedral oxides, where M is a metalselected from one of Groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14 and Lanthanide's of the Periodic Table of Elements, preferably M isselected from one of the group consisting of Si, Co, Cr, Cu, Fe, Ga, Ge,Mg, Mn, Ni, Sn, Ti, Zn and Zr. In an embodiment, m is greater than orequal to 0.2, and x, y and z are greater than or equal to 0.01. Inanother embodiment, m is greater than 0.1 to about 1, x is greater than0 to about 0.25, y is in the range of from 0.4 to 0.5, and z is in therange of from 0.25 to 0.5, more preferably m is from 0.15 to 0.7, x isfrom 0.01 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to 0.5.

[0045] Non-limiting examples of SAPO and AlPO molecular sieves usefulherein include one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16,SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37,SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Pat. No. 6,162,415), SAPO-47,SAPO-56, AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37,AlPO-46, and metal containing molecular sieves thereof. Of these,particularly useful molecular sieves are one or a combination ofSAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, AlPO-18 and AlPO-34 andmetal containing derivatives thereof, such as one or a combination ofSAPO-18, SAPO-34, AlPO-34 and AlPO-18, and metal containing derivativesthereof, and especially one or a combination of SAPO-34 and AlPO-18, andmetal containing derivatives thereof.

[0046] In an embodiment, the molecular sieve is an intergrowth materialhaving two or more distinct crystalline phases within one molecularsieve composition. In particular, intergrowth molecular sieves aredescribed in the U.S. patent application Ser. No. 09/924,016 filed Aug.7, 2001 and International Publication No. WO 98/15496 published Apr. 16,1998, both of which are herein fully incorporated by reference. Forexample, SAPO-18, AlPO-18 and RUW-18 have an AEI framework-type, andSAPO-34 has a CHA framework-type. Thus the molecular sieve used hereinmay comprise at least one intergrowth phase of AEI and CHAframework-types, especially where the ratio of CHA framework-type to AEIframework-type, as determined by the DIFFaX method disclosed in U.S.patent application Ser. No. 09/924,106 filed Aug. 7, 2001, is greaterthan 1:1.

Molecular Sieve Synthesis

[0047] The synthesis of molecular sieves is described in many of thereferences discussed above. Generally, molecular sieves are synthesizedby the hydrothermal crystallization of one or more of a source ofaluminum, a source of phosphorus, a source of silicon and a templatingagent, such as a nitrogen containing organic compound. Typically, acombination of sources of silicon, aluminum and phosphorus, optionallywith one or more templating agents, is placed in a sealed pressurevessel, optionally lined with an inert plastic such aspolytetrafluoroethylene, and heated, under a crystallization pressureand temperature, until a crystalline material is formed, and thenrecovered by filtration, centrifugation and/or decanting.

[0048] Non-limiting examples of silicon sources include silicates, fumedsilica, for example, Aerosil-200 available from Degussa Inc., New York,N.Y., and CAB-O-SIL M-5, organosilicon compounds such as tetraalkylorthosilicates, for example, tetramethyl orthosilicate (TMOS) andtetraethylorthosilicate (TEOS), colloidal silicas or aqueous suspensionsthereof, for example Ludox HS-40 sol available from E. I. du Pont deNemours, Wilmington, Del., silicic acid or any combination thereof.

[0049] Non-limiting examples of aluminum sources include aluminumalkoxides, for example aluminum isopropoxide, aluminum phosphate,aluminum hydroxide, sodium aluminate, pseudo-boehmite, gibbsite andaluminum trichloride, or any combination thereof. A convenient source ofaluminum is pseudo-boehmite, particularly when producing asilicoaluminophosphate molecular sieve.

[0050] Non-limiting examples of phosphorus sources, which may alsoinclude aluminum-containing phosphorus compositions, include phosphoricacid, organic phosphates such as triethyl phosphate, and crystalline oramorphous aluminophosphates such as AlPO₄, phosphorus salts, orcombinations thereof. A convenient source of phosphorus is phosphoricacid, particularly when producing a silicoaluminophosphate.

[0051] Templating agents are generally compounds that contain elementsof Group 15 of the Periodic Table of Elements, particularly nitrogen,phosphorus, arsenic and antimony. Typical templating agents also containat least one alkyl or aryl group, such as an alkyl or aryl group havingfrom 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms.Preferred templating agents are often nitrogen-containing compounds,such as amines, quaternary ammonium compounds and combinations thereof.Suitable quaternary ammonium compounds are represented by the generalformula R₄N⁺, where each R is hydrogen or a hydrocarbyl or substitutedhydrocarbyl group, preferably an alkyl group or an aryl group havingfrom 1 to 10 carbon atoms.

[0052] Non-limiting examples of templating agents include tetraalkylammonium compounds including salts thereof, such as tetramethyl ammoniumcompounds, tetraethyl ammonium compounds, tetrapropyl ammoniumcompounds, and tetrabutylammonium compounds, cyclohexylamine,morpholine, di-n-propylamine (DPA), tripropylamine, triethylamine (TEA),triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine,N,N-dimethylbenzylamine, N,N-diethylethanolamine, dicyclohexylamine,N,N-dimethylethanolamine, choline, N,N′-dimethylpiperazine,1,4-diazabicyclo(2,2,2)octane, N′,N′,N,N-tetramethyl-(1,6)hexanediamine,N-methyldiethanolamine, N-methyl-ethanolamine, N-methyl piperidine,3-methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine,4-methyl-pyridine, quinuclidine, N,N′-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine, neopentylamine, di-n-pentylamine,isopropylamine, t-butyl-amine, ethylenediamine, pyrrolidine, and2-imidazolidone.

[0053] The pH of the synthesis mixture containing at a minimum asilicon-, aluminum-, and/or phosphorus-composition, and a templatingagent, is generally in the range of from 2 to 10, such as from 4 to 9,for example from 5 to 8.

[0054] Generally, the synthesis mixture described above is sealed in avessel and heated, preferably under autogenous pressure, to atemperature in the range of from about 80° C. to about 250° C., such asfrom about 100° C. to about 250° C., for example from about 125° C. toabout 225° C., such as from about 150° C. to about 180° C.

[0055] In one embodiment, the synthesis of a molecular sieve is aided byseeds from another or the same framework type molecular sieve.

[0056] The time required to form the crystalline product is usuallydependent on the temperature and can vary from immediately up to severalweeks. Typically the crystallization time is from about 30 minutes toaround 2 weeks, such as from about 45 minutes to about 240 hours, forexample from about 1 hour to about 120 hours. The hydrothermalcrystallization may be carried out with or without agitation orstirring.

[0057] Once the crystalline molecular sieve product is formed, usuallyin a slurry state, it may be recovered by any standard technique wellknown in the art, for example, by centrifugation or filtration. Therecovered crystalline product may then be washed, such as with water,and then dried, such as in air.

[0058] One method for crystallization involves producing an aqueousreaction mixture containing an excess amount of a templating agent,subjecting the mixture to crystallization under hydrothermal conditions,establishing an equilibrium between molecular sieve formation anddissolution, and then, removing some of the excess templating agentand/or organic base to inhibit dissolution of the molecular sieve. Seefor example U.S. Pat. No. 5,296,208, which is herein fully incorporatedby reference.

[0059] Other methods for synthesizing molecular sieves or modifyingmolecular sieves are described in U.S. Pat. No. 5,879,655 (controllingthe ratio of the templating agent to phosphorus), U.S. Pat. No.6,005,155 (use of a modifier without a salt), U.S. Pat. No. 5,475,182(acid extraction), U.S. Pat. No. 5,962,762 (treatment with transitionmetal), U.S. Pat. Nos. 5,925,586 and 6,153,552 (phosphorus modified),U.S. Pat. No. 5,925,800 (monolith supported), U.S. Pat. No. 5,932,512(fluorine treated), U.S. Pat. No. 6,046,373 (electromagnetic wavetreated or modified), U.S. Pat. No. 6,051,746 (polynuclear aromaticmodifier), U.S. Pat. No. 6,225,254 (heating template), PCT WO 01/36329published May 25, 2001 (surfactant synthesis), PCT WO 01/25151 publishedApr. 12, 2001 (staged acid addition), PCT WO 01/60746 published Aug. 23,2001 (silicon oil), U.S. patent application Ser. No. 09/929,949 filedAug. 15, 2001 (cooling molecular sieve), U.S. patent application Ser.No. 09/615,526 filed Jul. 13, 2000 (metal impregnation includingcopper), U.S. patent application Ser. No. 09/672,469 filed Sep. 28, 2000(conductive microfilter), and U.S. patent application Ser. No.09/754,812 filed Jan. 4, 2001 (freeze drying the molecular sieve), whichare all herein fully incorporated by reference.

[0060] Where a templating agent is used in the synthesis of themolecular sieve, any templating agent retained in the product may beremoved after crystallization by numerous well known techniques, forexample, by calcination. Calcination involves contacting the molecularsieve containing the templating agent with a gas, preferably containingoxygen, at any desired concentration at an elevated temperaturesufficient to either partially or completely remove the templatingagent.

[0061] Aluminosilicate and silicoaluminophosphate molecular sieves haveeither a high silicon (Si) to aluminum (Al) ratio or a low silicon toaluminum ratio, however, a low Si/Al ratio is preferred for SAPOsynthesis. In one embodiment, the molecular sieve has a Si/Al ratio lessthan 0.65, such as less than 0.40, for example less than 0.32, andparticularly less than 0.20. In another embodiment the molecular sievehas a Si/Al ratio in the range of from about 0.65 to about 0.10, such asfrom about 0.40 to about 0.10, for example from about 0.32 to about0.10, and particularly from about 0.32 to about 0.15.

Active Metal Oxides

[0062] Active metal oxides useful herein are those metal oxides,different from typical binders and/or matrix materials, that, when usedin combination with a molecular sieve, provide benefits in catalyticconversion processes. Preferred active metal oxides are those metaloxides having a Group 4 metal, such as zirconium and/or hafnium, eitheralone or in combination with a Group 2 (for example magnesium, calcium,strontium and barium) and/or a Group 3 metal (including the Lanthanidesand Actinides) oxide (for example yttrium, scandium and lanthanum). Themost preferred active Group 4 metal oxide is an active zirconium metaloxide, either alone or in combination with calcium oxide, barium oxide,lanthanum oxide and/or yttrium oxide. In general, oxides of silicon,aluminum, and combinations thereof are not preferred.

[0063] In one embodiment, active metal oxides are those metal oxides,different from typical binders and/or matrix materials that, when usedin combination with a molecular sieve in a catalyst composition, areeffective in extending of the useful life of the catalyst composition.Quantification of the extension in catalyst life is determined by theLifetime Enhancement Index (LEI) as defined by the following equation:${LEI} = \frac{{\text{Lifetime}\quad {of}\quad {Catalyst}\quad {in}\quad {Combination}\quad {with}\quad {Active}\quad {Metal}\quad {Oxide}}\quad}{{Lifetime}\quad {of}\quad {Catalyst}}$

[0064] where the lifetime of the catalyst or catalyst composition, inthe same process under the same conditions, is the cumulative amount offeedstock processed per gram of catalyst composition until theconversion of feedstock by the catalyst composition falls below somedefined level, for example 10%. An inactive metal oxide will have littleto no effect on the lifetime of the catalyst composition, or willshorten the lifetime of the catalyst composition, and will thereforehave a LEI less than or equal to 1. Thus active metal oxides of theinvention are those metal oxides, different from typical binders and/ormatrix materials, that, when used in combination with a molecular sieve,provide a molecular sieve catalyst composition that has a LEI greaterthan 1. By definition, a molecular sieve catalyst composition that hasnot been combined with an active metal oxide will have a LEI equal to1.0.

[0065] It is found that, by including an active metal oxide incombination with a molecular sieve, a catalyst composition can beproduced having an LEI in the range of from greater than 1 to 20, suchas from about 1.5 to about 10. Typically catalyst compositions accordingto the invention exhibit LEI values greater than 1.1, for example in therange of from about 1.2 to 15, and more particularly greater than 1.3,such as greater than 1.5, such as greater than 1.7, such as greater than2.

[0066] In one embodiment, the active metal oxide when combined with amolecular sieve in a catalyst composition enhances the lifetime of thecatalyst composition in the conversion of a feedstock comprisingmethanol, preferably into one or more olefin(s).

[0067] In particular, the metal oxides useful herein have an uptake ofcarbon dioxide at 100° C. of at least 0.03 mg/m² of the metal oxide,such as at least 0.035 mg/m² of the metal oxide. Although the upperlimit on the carbon dioxide uptake of the metal oxide is not critical,in general the metal oxides useful herein will have a carbon dioxide at100° C. of less than 10 mg/m² of the metal oxide, such as less than 5mg/m² of the metal oxide. Typically, the metal oxides useful herein havea carbon dioxide uptake of 0.04 to 0.2 mg/m² of the metal oxide.

[0068] In order to determine the carbon dioxide uptake of a metal oxide,the following procedure is adopted. A sample of the metal oxide isdehydrated by heating the sample to about 200° C. to 500° C. in flowingair until a constant weight, the “dry weight”, is obtained. Thetemperature of the sample is then reduced to 100° C. and carbon dioxideis passed over the sample, either continuously or in pulses, again untilconstant weight is obtained. The increase in weight of the sample interms of mg/mg of the sample based on the dry weight of the sample isthe amount of adsorbed carbon dioxide.

[0069] In the Examples reported below, the carbon dioxide adsorption ismeasured using a Mettler TGA/SDTA 851 thermogravimetric analysis systemunder ambient pressure. The metal oxide sample is dehydrated in flowingair to about 500° C. for one hour. The temperature of the sample is thenreduced in flowing helium to 100° C. After the sample has equilibratedat the desired adsorption temperature in flowing helium, the sample issubjected to 20 separate pulses (about 12 seconds/pulse) of a gaseousmixture comprising 10-weight % carbon dioxide with the remainder beinghelium. After each pulse of the adsorbing gas the metal oxide sample isflushed with flowing helium for 3 minutes. The increase in weight of thesample in terms of mg/mg adsorbent based on the adsorbent weight aftertreatment at 500° C. is the amount of adsorbed carbon dioxide. Thesurface area of the sample is measured in accordance with the method ofBrunauer, Emmett, and Teller (BET) published as ASTM D 3663 to providethe carbon dioxide uptake in terms of mg carbon dioxide/m² of the metaloxide.

[0070] In one embodiment, the active metal oxide(s) has a BET surfacearea of greater than 10 m²/g, such as greater than 10 m²/g to about 300m²/g. In another embodiment, the active metal oxide(s) has a BET surfacearea greater than 20 m²/g, such as from 20 m²/g to 250 m²/g. In yetanother embodiment, the active metal oxide(s) has a BET surface areagreater than 25 m²/g, such as from 25 m²/g to about 200 m²/g. In apreferred embodiment, the active metal oxide(s) includes a zirconiumoxide having a BET surface area greater than 20 m²/g, such as greaterthan 25 m²/g and particularly greater than 30 m²/g

[0071] The active metal oxide(s) used herein can be prepared using avariety of methods. It is preferable that the active metal oxide is madefrom an active metal oxide precursor, such as a metal salt, such as ahalide, nitrate sulfate or acetate. Other suitable sources of the metaloxide include compounds that form the metal oxide during calcination,such as oxychlorides and nitrates. Alkoxides are also suitable sourcesof the Group 4 metal oxide, for example zirconium n-propoxide. Apreferred source of the Group 4 metal oxide is hydrated zirconia. Theexpression, hydrated zirconia, is intended to connote a materialcomprising zirconium atoms covalently linked to other zirconium atomsvia bridging oxygen atoms, and further comprising available hydroxylgroups.

[0072] In one embodiment, the hydrated zirconia is hydrothermallytreated under conditions that include a temperature of at least 80° C.,preferably at least 100° C. The hydrothermal treatment typically takesplace in a sealed vessel at greater than atmospheric pressure. However,a preferred mode of treatment involves the use of an open vessel underreflux conditions. Agitation of hydrated Group 4 metal oxide in a liquidmedium, for example, by the action of refluxing liquid and/or stirring,promotes the effective interaction of the hydrated oxide with the liquidmedium. The duration of the contact of the hydrated oxide with theliquid medium is conveniently at least 1 hour, such as at least 8 hours.The liquid medium for this treatment typically has a pH of about 6 orgreater, such as 8 or greater. Non-limiting examples of suitable liquidmedia include water, hydroxide solutions (including hydroxides of NH₄ ⁺,Na⁺, K⁺, Mg²⁺, and Ca²⁺), carbonate and bicarbonate solutions (includingcarbonates and bicarbonates of NH₄ ⁺, Na⁺, K⁺, Mg²⁺, and Ca²⁺), pyridineand its derivatives, and alkyl/hydroxyl amines.

[0073] In another embodiment, the active metal oxide is prepared, forexample, by subjecting a liquid solution, such as an aqueous solution,comprising a source of ions of a Group 4 metal to conditions sufficientto cause precipitation of a hydrated precursor of the solid oxidematerial, such as by the addition of a precipitating reagent to thesolution. Conveniently, the precipitation is conducted at a pH above 7.For example, the precipitating agent may be a base such as sodiumhydroxide or ammonium hydroxide.

[0074] When a mixture of a Group 4 metal oxide with a Group 2 and/or 3metal oxide is to be prepared, a first liquid solution comprising asource of ions of a Group 4 metal can be combined with a second liquidsolution comprising a source of ions of a Group 2 and/or Group 3 metal.This combination of two solutions can take place under conditionssufficient to cause co-precipitation of the mixed oxide material as asolid from the liquid medium. Alternatively, the source of ions of theGroup 4 metal and the source of ions of the Group 2 and/or Group 3 metalmay be combined into a single solution. This solution may then besubjected to conditions sufficient to cause co-precipitation of ahydrated precursor of the solid mixed oxide material, such as by theaddition of a precipitating reagent to the solution.

[0075] The temperature at which the liquid medium is maintained duringthe precipitation is generally less than about 200° C., such as in therange of from about 0° C. to about 200° C. A particular range oftemperatures for precipitation is from about 20° C. to about 100° C. Theresulting gel is preferably then hydrothermally treated at temperaturesof at least 80° C., preferably at least 100° C. The hydrothermaltreatment typically takes place in a vessel at atmospheric pressure. Thegel, in one embodiment, is hydrothermally treated for up to 10 days,such as up to 5 days, for example up to 3 days.

[0076] The hydrated precursor to the metal oxide(s) is then recovered,for example by filtration or centrifugation, and washed and dried. Theresulting material can then be calcined, such as in an oxidizingatmosphere, at a temperature of at least 400° C., such as at least 500°C., for example from about 600° C. to about 900° C., and particularlyfrom about 650° C. to about 800° C., to form the active metal oxide oractive mixed metal oxide. The calcination time is typically up to 48hours, such as for about 0.5 to 24 hours, for example for about 1.0 to10 hours. In one embodiment, calcination is carried out at about 700° C.for about 1 to about 3 hours.

[0077] In another embodiment, the Group 4 metal oxide and the Group 2and/or Group 3 metal oxide are made separately and then contactedtogether to form the mixed metal oxide that is then contacted with themolecular sieve. For example, the Group 4 metal oxide can be contactedwith the molecular sieve prior to introducing the Group 2 and/or Group 3metal oxide or alternatively, the Group 2 and/or Group 3 metal oxide canbe contacted with the molecular sieve prior to introducing the Group 4metal oxide.

[0078] Where the catalyst composition comprises a Group 4 metal oxideand a Group 3 metal oxide, the mole ratio of the Group 4 metal oxide tothe Group 3 metal oxide may be in the range of from 1000:1 to 1:1, suchas from about 500:1 to 2:1, such as from about 100:1 to about 3:1, suchas from about 75:1 to about 5:1 based on the total moles of the Group 4and Group 3 metal oxides. In addition, the catalyst composition cancontain from 1 to 25%, such as from 1 to 20%, such as from 1 to 15%, byweight of Group 3 metal based on the total weight of the mixed metaloxide, particularly where the Group 3 metal oxide is a lanthanum oryttrium metal oxide and the Group 4 metal oxide is a zirconium metaloxide.

[0079] Where the catalyst composition comprises a Group 4 metal oxideand a Group 2 metal oxide, the mole ratio of the Group 4 metal oxide tothe Group 2 metal oxide may be in the range of from 1000:1 to 1:2, suchas from about 500:1 to 2:3, such as from about 100:1 to about 1:1, suchas from about 50:1 to about 2:1, based on the total moles of the Group 4and Group 2 metal oxides. In addition, the catalyst composition cancontain from 1 to 25%, such as from 1 to 20%, such as from 1 to 15%, byweight of Group 2 metal based on the total weight of the mixed metaloxide, particularly where the Group 2 metal oxide is calcium oxide andthe Group 4 metal oxide is a zirconium metal oxide.

Catalyst Composition

[0080] The catalyst composition of the invention includes any one of themolecular sieves previously described and one or more of the activemetal oxides described above, optionally with a binder and/or matrixmaterial different from the active metal oxide(s). Typically, the weightratio of the molecular sieve to the active metal oxide(s) in thecatalyst composition is in the range of from 5 weight percent to 800weight percent, such as from 10 weight percent to 600 weight percent,particularly from 20 weight percent to 500 weight percent, and moreparticularly from 30 weight percent to 400 weight percent.

[0081] There are many different binders that are useful in formingcatalyst compositions. Non-limiting examples of binders that are usefulalone or in combination include various types of hydrated alumina,silicas, and/or other inorganic oxide sols. One preferred aluminacontaining sol is aluminum chlorhydrol. The inorganic oxide sol actslike glue binding the synthesized molecular sieves and other materialssuch as the matrix together, particularly after thermal treatment. Uponheating, the inorganic oxide sol, preferably having a low viscosity, isconverted into an inorganic oxide binder component. For example, analumina sol will convert to an aluminum oxide binder following heattreatment.

[0082] Aluminum chlorhydrol, a hydroxylated aluminum based solcontaining a chloride counter ion, has the general formula ofAl_(m)O_(n)(OH)_(o)Cl_(p)•x(H₂O) wherein m is 1 to 20, n is 1 to 8, o is5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binderis Al₁₃O₄(OH)₂₄Cl₇•12(H₂O) as is described in G. M. Wolterman, et al.,Stud. Surf. Sci. and Catal., 76, pages 105-144 (1993), which is hereinincorporated by reference. In another embodiment, one or more bindersare combined with one or more other non-limiting examples of aluminamaterials such as aluminum oxyhydroxide, γ-alumina, boehmite, diaspore,and transitional aluminas such as α-alumina, β-alumina, γ-alumina,δ-alumina, ε-alumina, κ-alumina, and ρ-alumina, aluminum trihydroxide,such as gibbsite, bayerite, nordstrandite, doyelite, and mixturesthereof.

[0083] In another embodiment, the binder is an alumina sol,predominantly comprising aluminum oxide, optionally including somesilicon. In yet another embodiment, the binder is peptized alumina madeby treating an alumina hydrate, such as pseudobohemite, with an acid,preferably an acid that does not contain a halogen, to prepare a sol oraluminum ion solution. Non-limiting examples of commercially availablecolloidal alumina sols include Nalco 8676 available from Nalco ChemicalCo., Naperville, Ill., and Nyacol AL20DW available from Nyacol NanoTechnologies, Inc., Ashland, Mass.

[0084] Where the catalyst composition contains a matrix material, thisis preferably different from the active metal oxide and any binder.Matrix materials are typically effective in reducing overall catalystcost, acting as thermal sinks to assist in shielding heat from thecatalyst composition for example during regeneration, densifying thecatalyst composition, and increasing catalyst strength such as crushstrength and attrition resistance.

[0085] Non-limiting examples of matrix materials include one or morenon-active metal oxides including beryllia, quartz, silica or sols, andmixtures thereof, for example silica-magnesia, silica-zirconia,silica-titania, silica-alumina and silica-alumina-thoria. In anembodiment, matrix materials are natural clays such as those from thefamilies of montmorillonite and kaolin. These natural clays includesubbentonites and those kaolins known as, for example, Dixie, McNamee,Georgia and Florida clays. Non-limiting examples of other matrixmaterials include haloysite, kaolinite, dickite, nacrite, or anauxite.The matrix material, such as a clay, may be subjected to well knownmodification processes such as calcination and/or acid treatment and/orchemical treatment.

[0086] In a preferred embodiment, the matrix material is a clay or aclay-type composition, particularly a clay or clay-type compositionhaving a low iron or titania content, and most preferably the matrixmaterial is kaolin. Kaolin has been found to form a pumpable, highsolids content slurry, to have a low fresh surface area, and to packtogether easily due to its platelet structure. A preferred averageparticle size of the matrix material, most preferably kaolin, is fromabout 0.1 μm to about 0.6 μm with a D₉₀ particle size distribution ofless than about 1 μm.

[0087] Where the catalyst composition contains a binder or matrixmaterial, the catalyst composition typically contains from about 1% toabout 80%, such as from about 5% to about 60%, and particularly fromabout 5% to about 50%, by weight of the molecular sieve based on thetotal weight of the catalyst composition.

[0088] Where the catalyst composition contains a binder and a matrixmaterial, the weight ratio of the binder to the matrix material istypically from 1:15 to 1:5, such as from 1:10 to 1:4, and particularlyfrom 1:6 to 1:5. The amount of binder is typically from about 2% byweight to about 30% by weight, such as from about 5% by weight to about20% by weight, and particularly from about 7% by weight to about 15% byweight, based on the total weight of the binder, the molecular sieve andmatrix material. It has been found that a higher sieve content and lowermatrix content increases the molecular sieve catalyst compositionperformance, whereas a lower sieve content and higher matrix contentimproves the attrition resistance of the composition.

[0089] The catalyst composition typically has a density in the range offrom 0.5 g/cc to 5 g/cc, such as from from 0.6 g/cc to 5 g/cc, forexample from 0.7 g/cc to 4 g/cc, particularly in the range of from 0.8g/cc to 3 g/cc.

Method of Making the Catalyst Composition

[0090] In making the catalyst composition, the molecular sieve is firstformed and is then physically mixed with the active metal oxide,preferably in a substantially dry, dried, or calcined state. Mostpreferably the molecular sieve and active metal oxides are physicallymixed in their calcined state. Without being bound by any particulartheory, it is believed that intimate mixing of the molecular sieve andone or more active metal oxides improves conversion processes using themolecular sieve composition and catalyst composition of the invention.Intimate mixing can be achieved by any method known in the art, such asmixing with a mixer muller, drum mixer, ribbon/paddle blender, kneader,or the like. Chemical reaction between the molecular sieve and the metaloxide(s) is unnecessary and, in general, is not preferred.

[0091] Where the catalyst composition contains a matrix and/or binder,the molecular sieve is conveniently initially formulated into a catalystprecursor with the matrix and/or binder and the active metal oxide isthen combined with the formulated precursor. The active metal oxide canbe added as unsupported particles or can be added in combination with asupport, such as a binder or matrix material. The resultant catalystcomposition can then be formed into useful shaped and sized particles bywell-known techniques such as spray drying, pelletizing, extrusion, andthe like.

[0092] In one embodiment, the molecular sieve composition and the matrixmaterial, optionally with a binder, are combined with a liquid to form aslurry and then mixed, preferably rigorously mixed, to produce asubstantially homogeneous mixture containing the molecular sievecomposition. Non-limiting examples of suitable liquids include one or acombination of water, alcohol, ketones, aldehydes, and/or esters. Themost preferred liquid is water. In one embodiment, the slurry iscolloid-milled for a period of time sufficient to produce the desiredslurry texture, sub-particle size, and/or sub-particle sizedistribution.

[0093] The molecular sieve composition and matrix material, and theoptional binder, can be combined in the same or different liquids, andcan be combined in any order, together, simultaneously, sequentially, ora combination thereof. In the preferred embodiment, the same liquid,preferably water is used. The molecular sieve composition, matrixmaterial, and optional binder, are combined in a liquid as solids,substantially dry or in a dried form, or as slurries, together orseparately. If solids are added together as dry or substantially driedsolids, it is preferable to add a limited and/or controlled amount ofliquid.

[0094] In one embodiment, the slurry of the molecular sieve composition,binder and matrix materials is mixed or milled to achieve a sufficientlyuniform slurry of sub-particles of the molecular sieve catalystcomposition that is then fed to a forming unit that produces themolecular sieve catalyst composition. In a preferred embodiment, theforming unit is spray dryer. Typically, the forming unit is maintainedat a temperature sufficient to remove most of the liquid from theslurry, and from the resulting molecular sieve catalyst composition. Theresulting catalyst composition when formed in this way takes the form ofmicrospheres.

[0095] When a spray drier is used as the forming unit, typically, theslurry of the molecular sieve composition and matrix material, andoptionally a binder, is co-fed to the spray drying volume with a dryinggas with an average inlet temperature ranging from 200° C. to 550° C.,and a combined outlet temperature ranging from 100° C. to about 225° C.In an embodiment, the average diameter of the spray dried formedcatalyst composition is from about 40 μm to about 300 μm, such as fromabout 50 μm to about 250 μm, for example from about 50 μm to about 200μm, and conveniently from about 65 μm to about 90 μm.

[0096] Other methods for forming a molecular sieve catalyst compositionare described in U.S. patent application Ser. No. 09/617,714 filed Jul.17, 2000 (spray drying using a recycled molecular sieve catalystcomposition), which is herein incorporated by reference.

[0097] Once the molecular sieve catalyst composition is formed in asubstantially dry or dried state, to further harden and/or activate theformed catalyst composition, a heat treatment such as calcination, at anelevated temperature is usually performed. Typical calcinationtemperatures are in the range from about 400° C. to about 1,000° C.,such as from about 500° C. to about 800° C., such as from about 550° C.to about 700° C. Typical calcination environments are air (which mayinclude a small amount of water vapor), nitrogen, helium, flue gas(combustion product lean in oxygen), or any combination thereof.

[0098] In a preferred embodiment, the catalyst composition is heated innitrogen at a temperature of from about 600° C. to about 700° C. Heatingis carried out for a period of time typically from 30 minutes to 15hours, such as from 1 hour to about 10 hours, for example from about 1hour to about 5 hours, and particularly from about 2 hours to about 4hours.

Process for Using the Molecular Sieve Catalyst Compositions

[0099] The catalyst compositions described above are useful in a varietyof processes including cracking, of for example a naphtha feed to lightolefin(s) (U.S. Pat. No. 6,300,537) or higher molecular weight (MW)hydrocarbons to lower MW hydrocarbons; hydrocracking, of for exampleheavy petroleum and/or cyclic feedstock; isomerization, of for examplearomatics such as xylene; polymerization, of for example one or moreolefin(s) to produce a polymer product; reforming; hydrogenation;dehydrogenation; dewaxing, of for example hydrocarbons to removestraight chain paraffins; absorption, of for example alkyl aromaticcompounds for separating out isomers thereof; alkylation, of for examplearomatic hydrocarbons such as benzene and alkyl benzene, optionally withpropylene to produce cumene or with long chain olefins; transalkylation,of for example a combination of aromatic and polyalkylaromatichydrocarbons; dealkylation; hydrodecylization; disproportionation, offor example toluene to make benzene and paraxylene; oligomerization, offor example straight and branched chain olefin(s); anddehydrocyclization.

[0100] Preferred processes include processes for converting naphtha tohighly aromatic mixtures; converting light olefin(s) to gasoline,distillates and lubricants; converting oxygenates to olefin(s);converting light paraffins to olefins and/or aromatics; and convertingunsaturated hydrocarbons (ethylene and/or acetylene) to aldehydes forconversion into alcohols, acids and esters.

[0101] The most preferred process of the invention is a process directedto the conversion of a feedstock to one or more olefin(s). Typically,the feedstock contains one or more aliphatic-containing compounds suchthat the aliphatic moiety contains from 1 to about 50 carbon atoms, suchas from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms, andparticularly from 1 to 4 carbon atoms.

[0102] Non-limiting examples of aliphatic-containing compounds includealcohols such as methanol and ethanol, alkyl mercaptans such as methylmercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide,alkylamines such as methylamine, alkyl ethers such as dimethyl ether,diethyl ether and methylethyl ether, alkyl halides such as methylchloride and ethyl chloride, alkyl ketones such as dimethyl ketone,formaldehydes, and various acids such as acetic acid.

[0103] In a preferred embodiment of the process of the invention, thefeedstock contains one or more oxygenates, more specifically, one ormore organic compound(s) containing at least one oxygen atom. In themost preferred embodiment of the process of invention, the oxygenate inthe feedstock is one or more alcohol(s), preferably aliphatic alcohol(s)where the aliphatic moiety of the alcohol(s) has from 1 to 20 carbonatoms, preferably from 1 to 10 carbon atoms, and most preferably from 1to 4 carbon atoms. The alcohols useful as feedstock in the process ofthe invention include lower straight and branched chain aliphaticalcohols and their unsaturated counterparts.

[0104] Non-limiting examples of oxygenates include methanol, ethanol,n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethylether, di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethylketone, acetic acid, and mixtures thereof.

[0105] In the most preferred embodiment, the feedstock is selected fromone or more of methanol, ethanol, dimethyl ether, diethyl ether or acombination thereof, more preferably methanol and dimethyl ether, andmost preferably methanol.

[0106] The various feedstocks discussed above, particularly a feedstockcontaining an oxygenate, more particularly a feedstock containing analcohol, is converted primarily into one or more olefin(s). Theolefin(s) produced from the feedstock typically have from 2 to 30 carbonatoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbonatoms, still more preferably 2 to 4 carbons atoms, and most preferablyare ethylene and/or propylene.

[0107] The catalyst composition of the invention is particularly usefulin the process that is generally referred to as the gas-to-olefins (GTO)process or alternatively, the methanol-to-olefins (MTO) process. In thisprocess, an oxygenated feedstock, most preferably a methanol-containingfeedstock, is converted in the presence of a molecular sieve catalystcomposition into one or more olefin(s), preferably and predominantly,ethylene and/or propylene.

[0108] Using the catalyst composition of the invention for theconversion of a feedstock, preferably a feedstock containing one or moreoxygenates, the amount of olefin(s) produced based on the total weightof hydrocarbon produced is greater than 50 weight percent, typicallygreater than 60 weight percent, such as greater than 70 weight percent,and preferably greater than 80 weight percent. Moreover, the amount ofethylene and/or propylene produced based on the total weight ofhydrocarbon product produced is greater than 40 weight percent,typically greater than 50 weight percent, for example greater than 65weight percent, and preferably greater than 78 weight percent.Typically, the amount ethylene produced in weight percent based on thetotal weight of hydrocarbon product produced, is greater than 20 weightpercent, such as greater than 30 weight percent, for example greaterthan 40 weight percent. In addition, the amount of propylene produced inweight percent based on the total weight of hydrocarbon product producedis typically greater than 20 weight percent, such as greater than 25weight percent, for example greater than 30 weight percent, andpreferably greater than 35 weight percent.

[0109] Using the catalyst composition of the invention for theconversion of a feedstock comprising methanol and dimethylether toethylene and propylene, it is found that the production of ethane andpropane is reduced by greater than 10%, such as greater than 20%, forexample greater than 30%, and particularly in the range of from about30% to 40% compared to a similar catalyst composition at the sameconversion conditions but without the active metal oxide component(s).

[0110] In addition to the oxygenate component, such as methanol, thefeedstock may contains one or more diluent(s), which are generallynon-reactive to the feedstock or molecular sieve catalyst compositionand are typically used to reduce the concentration of the feedstock.Non-limiting examples of diluents include helium, argon, nitrogen,carbon monoxide, carbon dioxide, water, essentially non-reactiveparaffins (especially alkanes such as methane, ethane, and propane),essentially non-reactive aromatic compounds, and mixtures thereof. Themost preferred diluents are water and nitrogen, with water beingparticularly preferred.

[0111] The diluent, for example water, may be used either in a liquid ora vapor form, or a combination thereof. The diluent may be either addeddirectly to the feedstock entering a reactor or added directly to thereactor, or added with the molecular sieve catalyst composition.

[0112] The present process can be conducted over a wide range oftemperatures, such as in the range of from about 200° C. to about 1000°C., for example from about 250° C. to about 800° C., including fromabout 250° C. to about 750° C., conveniently from about 300° C. to about650° C., typically from about 350° C. to about 600° C. and particularlyfrom about 350° C. to about 550° C.

[0113] Similarly, the present process can be conducted over a wide rangeof pressures including autogenous pressure. Typically the partialpressure of the feedstock exclusive of any diluent therein employed inthe process is in the range of from about 0.1 kPaa to about 5 MPaa, suchas from about 5 kPaa to about 1 MPaa, and conveniently from about 20kPaa to about 500 kPaa.

[0114] The weight hourly space velocity (WHSV), defined as the totalweight of feedstock excluding any diluents per hour per weight ofmolecular sieve in the catalyst composition, typically ranges from about1 hr−1 to about 5000 hr−1, such as from about 2 hr−1 to about 3000 hr−1,for example from about 5 hr−1 to about 1500 hr−1, and conveniently fromabout 10 hr−1 to about 1000 hr−1. In one embodiment, the WHSV is greaterthan 20 hr−1 and, where feedstock contains methanol and/or dimethylether, is in the range of from about 20 hr−1 to about 300 hr−1.

[0115] Where the process is conducted in a fluidized bed, thesuperficial gas velocity (SGV) of the feedstock including diluent andreaction products within the reactor system, and particularly within ariser reactor(s), is at least 0.1 meter per second (m/sec), such asgreater than 0.5 m/sec, such as greater than 1 m/sec, for examplegreater than 2 m/sec, conveniently greater than 3 m/sec, and typicallygreater than 4 m/sec. See for example U.S. patent application Ser. No.09/708,753 filed Nov. 8, 2000, which is herein incorporated byreference.

[0116] The process of the invention is conveniently conducted as a fixedbed process, or more typically as a fluidized bed process (including aturbulent bed process), such as a continuous fluidized bed process, andparticularly a continuous high velocity fluidized bed process.

[0117] The process can take place in a variety of catalytic reactorssuch as hybrid reactors that have a dense bed or fixed bed reactionzones and/or fast fluidized bed reaction zones coupled together,circulating fluidized bed reactors, riser reactors, and the like.Suitable conventional reactor types are described in for example U.S.Pat. No. 4,076,796, U.S. Pat. No. 6,287,522 (dual riser), andFluidization Engineering, D. Kunii and O. Levenspiel, Robert E. KriegerPublishing Company, New York, N.Y. 1977, which are all herein fullyincorporated by reference.

[0118] The preferred reactor types are riser reactors generallydescribed in Riser Reactor, Fluidization and Fluid-Particle Systems,pages 48 to 59, F. A. Zenz and D. F. Othmo, Reinhold PublishingCorporation, New York, 1960, and U.S. Pat. No. 6,166,282 (fast-fluidizedbed reactor), and U.S. patent application Ser. No. 09/564,613 filed May4, 2000 (multiple riser reactor), which are all herein fullyincorporated by reference.

[0119] In one practical embodiment, the process is conducted as afluidized bed process or high velocity fluidized bed process utilizing areactor system, a regeneration system and a recovery system.

[0120] In such a process the reactor system would conveniently include afluid bed reactor system having a first reaction zone within one or moreriser reactor(s) and a second reaction zone within at least onedisengaging vessel, typically comprising one or more cyclones. In oneembodiment, the one or more riser reactor(s) and disengaging vessel arecontained within a single reactor vessel. Fresh feedstock, preferablycontaining one or more oxygenates, optionally with one or morediluent(s), is fed to the one or more riser reactor(s) into which amolecular sieve catalyst composition or coked version thereof isintroduced. In one embodiment, prior to being introduced to the riserreactor(s), the molecular sieve catalyst composition or coked versionthereof is contacted with a liquid, preferably water or methanol, and/ora gas, for example, an inert gas such as nitrogen.

[0121] In an embodiment, the amount of fresh feedstock fed as a liquidand/or a vapor to the reactor system is in the range of from 0.1 weightpercent to about 85 weight percent, such as from about 1 weight percentto about 75 weight percent, more typically from about 5 weight percentto about 65 weight percent based on the total weight of the feedstockincluding any diluent contained therein. The liquid and vapor feedstocksmay be the same composition, or may contain varying proportions of thesame or different feedstocks with the same or different diluents.

[0122] The feedstock entering the reactor system is preferablyconverted, partially or fully, in the first reactor zone into a gaseouseffluent that enters the disengaging vessel along with the cokedcatalyst composition. In the preferred embodiment, cyclone(s) areprovided within the disengaging vessel to separate the coked catalystcomposition from the gaseous effluent containing one or more olefin(s)within the disengaging vessel. Although cyclones are preferred, gravityeffects within the disengaging vessel can also be used to separate thecatalyst composition from the gaseous effluent. Other methods forseparating the catalyst composition from the gaseous effluent includethe use of plates, caps, elbows, and the like.

[0123] In one embodiment, the disengaging vessel includes a strippingzone, typically in a lower portion of the disengaging vessel. In thestripping zone the coked catalyst composition is contacted with a gas,preferably one or a combination of steam, methane, carbon dioxide,carbon monoxide, hydrogen, or an inert gas such as argon, preferablysteam, to recover adsorbed hydrocarbons from the coked catalystcomposition that is then introduced to the regeneration system.

[0124] The coked catalyst composition is withdrawn from the disengagingvessel and introduced to the regeneration system. The regenerationsystem comprises a regenerator where the coked catalyst composition iscontacted with a regeneration medium, preferably a gas containingoxygen, under conventional regeneration conditions of temperature,pressure and residence time.

[0125] Non-limiting examples of suitable regeneration media include oneor more of oxygen, O3, SO3, N2O, NO, NO2, N2O5, air, air diluted withnitrogen or carbon dioxide, oxygen and water (U.S. Pat. No. 6,245,703),carbon monoxide and/or hydrogen. Suitable regeneration conditions arethose capable of burning coke from the coked catalyst composition,preferably to a level less than 0.5 weight percent based on the totalweight of the coked molecular sieve catalyst composition entering theregeneration system. For example, the regeneration temperature may be inthe range of from about 200° C. to about 1500° C., such as from about300° C. to about 1000° C., for example from about 450° C. to about 750°C., and conveniently from about 550° C. to 700° C. The regenerationpressure may be in the range of from about 15 psia (103 kPaa) to about500 psia (3448 kPaa), such as from about 20 psia (138 kPaa) to about 250psia (1724 kPaa), including from about 25 psia (172kPaa) to about 150psia (1034 kPaa), and conveniently from about 30 psia (207 kPaa) toabout 60 psia (414 kPaa).

[0126] The residence time of the catalyst composition in the regeneratormay be in the range of from about one minute to several hours, such asfrom about one minute to 100 minutes, and the volume of oxygen in theregeneration gas may be in the range of from about 0.01 mole percent toabout 5 mole percent based on the total volume of the gas.

[0127] The burning of coke in the regeneration step is an exothermicreaction, and in an embodiment, the temperature within the regenerationsystem is controlled by various techniques in the art including feedinga cooled gas to the regenerator vessel, operated either in a batch,continuous, or semi-continuous mode, or a combination thereof. Apreferred technique involves withdrawing the regenerated catalystcomposition from the regeneration system and passing it through acatalyst cooler to form a cooled regenerated catalyst composition. Thecatalyst cooler, in an embodiment, is a heat exchanger that is locatedeither internal or external to the regeneration system. Other methodsfor operating a regeneration system are disclosed in U.S. Pat. No.6,290,916 (controlling moisture), which is herein fully incorporated byreference.

[0128] The regenerated catalyst composition withdrawn from theregeneration system, preferably from a catalyst cooler, is combined witha fresh molecular sieve catalyst composition and/or re-circulatedmolecular sieve catalyst composition and/or feedstock and/or fresh gasor liquids, and returned to the riser reactor(s). In one embodiment, theregenerated catalyst composition withdrawn from the regeneration systemis returned to the riser reactor(s) directly, preferably after passingthrough a catalyst cooler. A carrier, such as an inert gas, feedstockvapor, steam or the like, may be used, semi-continuously orcontinuously, to facilitate the introduction of the regenerated catalystcomposition to the reactor system, preferably to the one or more riserreactor(s).

[0129] By controlling the flow of the regenerated catalyst compositionor cooled regenerated catalyst composition from the regeneration systemto the reactor system, the optimum level of coke on the molecular sievecatalyst composition entering the reactor is maintained. There are manytechniques for controlling the flow of a catalyst composition describedin Michael Louge, Experimental Techniques, Circulating Fluidized Beds,Grace, Avidan and Knowlton, eds., Blackie, 1997 (336-337), which isherein incorporated by reference.

[0130] Coke levels on the catalyst composition are measured bywithdrawing the catalyst composition from the conversion process anddetermining its carbon content. Typical levels of coke on the molecularsieve catalyst composition, after regeneration, are in the range of from0.01 weight percent to about 15 weight percent, such as from about 0.1weight percent to about 10 weight percent, for example from about 0.2weight percent to about 5 weight percent, and conveniently from about0.3 weight percent to about 2 weight percent based on the weight of themolecular sieve.

[0131] The gaseous effluent is withdrawn from the disengaging system andis passed through a recovery system. There are many well known recoverysystems, techniques and sequences that are useful in separatingolefin(s) and purifying olefin(s) from the gaseous effluent. Recoverysystems generally comprise one or more or a combination of variousseparation, fractionation and/or distillation towers, columns,splitters, or trains, reaction systems such as ethylbenzene manufacture(U.S. Pat. No. 5,476,978) and other derivative processes such asaldehydes, ketones and ester manufacture (U.S. Pat. No. 5,675,041), andother associated equipment, for example various condensers, heatexchangers, refrigeration systems or chill trains, compressors,knock-out drums or pots, pumps, and the like.

[0132] Non-limiting examples of these towers, columns, splitters ortrains used alone or in combination include one or more of ademethanizer, preferably a high temperature demethanizer, ade-ethanizer, a depropanizer, a wash tower often referred to as acaustic wash tower and/or quench tower, absorbers, adsorbers, membranes,ethylene (C2) splitter, propylene (C3) splitter, butene (C4) splitter,and the like.

[0133] Various recovery systems useful for recovering predominantlyolefin(s), preferably light olefin(s) such as ethylene, propylene and/orbutene, are described in U.S. Pat. No. 5,960,643 (secondary richethylene stream), U.S. Pat. Nos. 5,019,143, 5,452,581 and 5,082,481(membrane separations), U.S. Pat. No. 5,672,197 (pressure dependentadsorbents), U.S. Pat. No. 6,069,288 (hydrogen removal), U.S. Pat. No.5,904,880 (recovered methanol to hydrogen and carbon dioxide in onestep), U.S. Pat. No. 5,927,063 (recovered methanol to gas turbine powerplant), and U.S. Pat. No. 6,121,504 (direct product quench), U.S. Pat.No. 6,121,503 (high purity olefins without superfractionation), and U.S.Pat. No. 6,293,998 (pressure swing adsorption), which are all hereinfully incorporated by reference.

[0134] Other recovery systems that include purification systems, forexample for the purification of olefin(s), are described in Kirk-OthmerEncyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley &Sons, 1996, pages 249-271 and 894-899, which is herein incorporated byreference. Purification systems are also described in for example, U.S.Pat. No. 6,271,428 (purification of a diolefin hydrocarbon stream), U.S.Pat. No. 6,293,999 (separating propylene from propane), and U.S. patentapplication Ser. No. 09/689,363 filed Oct. 20, 2000 (purge stream usinghydrating catalyst), which are herein incorporated by reference.

[0135] Generally accompanying most recovery systems is the production,generation or accumulation of additional products, by-products and/orcontaminants along with the preferred prime products. The preferredprime products, the light olefins, such as ethylene and propylene, aretypically purified for use in derivative manufacturing processes such aspolymerization processes. Therefore, in the most preferred embodiment ofthe recovery system, the recovery system also includes a purificationsystem. For example, the light olefin(s) produced particularly in a MTOprocess are passed through a purification system that removes low levelsof by-products or contaminants.

[0136] Non-limiting examples of contaminants and by-products includegenerally polar compounds such as water, alcohols, carboxylic acids,ethers, carbon oxides, sulfur compounds such as hydrogen sulfide,carbonyl sulfides and mercaptans, ammonia and other nitrogen compounds,arsine, phosphine and chlorides. Other contaminants or by-productsinclude hydrogen and hydrocarbons such as acetylene, methyl acetylene,propadiene, butadiene and butyne.

[0137] Typically, in converting one or more oxygenates to olefin(s)having 2 or 3 carbon atoms, a minor amount hydrocarbons, particularlyolefin(s), having 4 or more carbon atoms is also produced. The amount ofC4+ hydrocarbons is normally less than 20 weight percent, such as lessthan 10 weight percent, for example less than 5 weight percent, andparticularly less than 2 weight percent, based on the total weight ofthe effluent gas withdrawn from the process, excluding water. Typically,therefore the recovery system may include one or more reaction systemsfor converting the C4+ impurities to useful products.

[0138] Non-limiting examples of such reaction systems are described inU.S. Pat. No. 5,955,640 (converting a four carbon product intobutene-1), U.S. Pat. No. 4,774,375 (isobutane and butene-2 oligomerizedto an alkylate gasoline), U.S. Pat. No. 6,049,017 (dimerization ofn-butylene), U.S. Pat. Nos. 4,287,369 and 5,763,678 (carbonylation orhydroformulation of higher olefins with carbon dioxide and hydrogenmaking carbonyl compounds), U.S. Pat. No. 4,542,252 (multistageadiabatic process), U.S. Pat. No. 5,634,354 (olefin-hydrogen recovery),and Cosyns, J. et al., Process for Upgrading C3, C4 and C5 OlefinicStreams, Pet. & Coal, Vol. 37, No. 4 (1995) (dimerizing or oligomerizingpropylene, butylene and pentylene), which are all herein fullyincorporated by reference.

[0139] The preferred light olefin(s) produced by any one of theprocesses described above are high purity prime olefin(s) products thatcontain a single carbon number olefin in an amount greater than 80percent, such as greater than 90 weight percent, such as greater than 95weight percent, for example at least about 99 weight percent, based onthe total weight of the olefin.

[0140] In one practical embodiment, the process of the invention formspart of an integrated process for producing light olefin(s) from ahydrocarbon feedstock, preferably a gaseous hydrocarbon feedstock,particularly methane and/or ethane. The first step in the process ispassing the gaseous feedstock, preferably in combination with a waterstream, to a syngas production zone to produce a synthesis gas (syngas)stream, typically comprising carbon dioxide, carbon monoxide andhydrogen. Syngas production is well known, and typical syngastemperatures are in the range of from about 700° C. to about 1200° C.and syngas pressures are in the range of from about 2 MPa to about 100MPa. Synthesis gas streams are produced from natural gas, petroleumliquids, and carbonaceous materials such as coal, recycled plastic,municipal waste or any other organic material. Preferably synthesis gasstream is produced via steam reforming of natural gas.

[0141] The next step in the process involves contacting the synthesisgas stream generally with a heterogeneous catalyst, typically a copperbased catalyst, to produce an oxygenate containing stream, often incombination with water. In one embodiment, the contacting step isconducted at temperature in the range of from about 150° C. to about450° C. and a pressure in the range of from about 5 MPa to about 10 MPa.

[0142] This oxygenate containing stream, or crude methanol, typicallycontains the alcohol product and various other components such asethers, particularly dimethyl ether, ketones, aldehydes, dissolved gasessuch as hydrogen methane, carbon oxide and nitrogen, and fuel oil. Theoxygenate containing stream, crude methanol, in the preferred embodimentis passed through a well known purification processes, distillation,separation and fractionation, resulting in a purified oxygenatecontaining stream, for example, commercial Grade A and AA methanol.

[0143] The oxygenate containing stream or purified oxygenate containingstream, optionally with one or more diluents, can then be used as afeedstock in a process to produce light olefin(s), such as ethyleneand/or propylene. Non-limiting examples of this integrated process aredescribed in EP-B-0 933 345, which is herein fully incorporated byreference.

[0144] In another more fully integrated process, that optionally iscombined with the integrated processes described above, the olefin(s)produced are directed to, in one embodiment, one or more polymerizationprocesses for producing various polyolefins. (See for example U.S.patent application Ser. No. 09/615,376 filed Jul. 13, 2000, which isherein fully incorporated by reference.)

[0145] Polymerization processes include solution, gas phase, slurryphase and a high pressure processes, or a combination thereof.Particularly preferred is a gas phase or a slurry phase polymerizationof one or more olefin(s) at least one of which is ethylene or propylene.These polymerization processes utilize a polymerization catalyst thatcan include any one or a combination of the molecular sieve catalystsdiscussed above, however, the preferred polymerization catalysts are theZiegler-Natta, Phillips-type, metallocene, metallocene-type and advancedpolymerization catalysts, and mixtures thereof.

[0146] In a preferred embodiment, the integrated process comprises aprocess for polymerizing one or more olefin(s) in the presence of apolymerization catalyst system in a polymerization reactor to produceone or more polymer products, wherein the one or more olefin(s) havebeen made by converting an alcohol, particularly methanol, using amolecular sieve catalyst composition as described above. The preferredpolymerization process is a gas phase polymerization process and atleast one of the olefins(s) is either ethylene or propylene, andpreferably the polymerization catalyst system is a supported metallocenecatalyst system. In this embodiment, the supported metallocene catalystsystem comprises a support, a metallocene or metallocene-type compoundand an activator, preferably the activator is a non-coordinating anionor alumoxane, or combination thereof, and most preferably the activatoris alumoxane.

[0147] The polymers produced by the polymerization processes describedabove include linear low density polyethylene, elastomers, plastomers,high density polyethylene, low density polyethylene, polypropylene andpolypropylene copolymers. The propylene based polymers produced by thepolymerization processes include atactic polypropylene, isotacticpolypropylene, syndiotactic polypropylene, and propylene random, blockor impact copolymers.

EXAMPLES

[0148] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingExamples are offered.

[0149] In the Examples, LEI is defined as the ratio of the lifetime of amolecular sieve catalyst composition containing an active metal oxide(s)compared to that of the same molecular sieve in the absence of a metaloxide, defined as having an LEI of 1. For the purpose of determiningLEI, lifetime is defined as the cumulative amount of oxygenateconverted, preferably into one or more olefin(s), per gram of molecularsieve, until the conversion rate drops to about 10% of its initialvalue. If the conversion has not fallen to 10% of its initial value bythe end of the experiment, lifetime is estimated by linear extrapolationbased on the rate of decrease in conversion over the last two datapoints in the experiment. For the purposes of determining the LEI forthe following Examples in a preferred oxygenate conversion process,methanol is converted to one or more olefin(s) at 475° C., 25 psig (172kPag) and a methanol weight hourly space velocity of 100 h−1.

[0150] “Prime Olefin” is the sum of the selectivity to ethylene andpropylene. The ratio “C2=/C3=” is the ratio of the ethylene to propyleneselectivity weighted over the run. The “C3 Purity” is calculated bydividing the propylene selectivity by the sum of the propylene andpropane selectivities. The selectivities for methane, ethylene, ethane,propylene, propane, C4's and C5+'s are average selectivities weightedover the run. Note that the C5+'s consist only of C5's, C6's and C7's.The selectivity values do not sum to 100% in the Tables because theyhave been corrected for coke as is well known.

Example A Preparation of Molecular Sieve

[0151] A silicoaluminophosphate molecular sieve, SAPO-34, designated asMSA, was crystallized in the presence of tetraethyl ammonium hydroxide(R1) and dipropylamine (R2) as the organic structure directing agents ortemplating agents. A mixture of the following mole ratio composition:

0.2 SiO₂/Al₂O₃/P₂O₅/0.9 R1/1.5 R2 /50 H₂O.

[0152] was prepared by initially mixing an amount of Condea Pural SBwith deionised water, to form a slurry. To this slurry was added anamount of phosphoric acid (85%). These additions were made with stirringto form a homogeneous mixture. To this homogeneous mixture Ludox AS40(40% of SiO2) was added, followed by the addition of R1 with mixing toform a homogeneous mixture. To this homogeneous mixture R2 was added.This homogeneous mixture was then crystallized with agitation in astainless steel autoclave by heating to 170° C. for 40 hours. Thisprovided a slurry of the crystalline molecular sieve. The crystals werethen separated from the mother liquor by filtration. The molecular sievecrystals were then mixed with a binder and matrix material and formedinto particles by spray drying.

Example B Conversion Process

[0153] All catalytic or conversion data presented was obtained using amicroflow reactor consisting of a stainless steel reactor (¼ inch (0.64cm) outer diameter) located in a furnace to which vaporized methanol wasfed. The reactor was maintained at a temperature of 475° C. and apressure of 25 psig (172.4 kPag) The flow rate of the methanol was suchthat the flow rate of methanol on weight basis per gram of molecularsieve, also known as the weight hourly space velocity (WHSV) was 100h−1. Product gases exiting the reactor were collected and analyzed usinggas chromatography. The catalyst load in each experiment was 50 mg andthe reactor bed was diluted with quartz to minimize hot spots in thereactor. In particular, for the catalyst composition of the invention, aphysical mixture of the MSA molecular sieve of Example A and the activemetal oxide(s) was used. The total catalyst composition load remained 50mg, and the methanol flow rate was adjusted as the amount of molecularsieve in the reactor bed was reduced by the addition of the mixed metaloxide such that the methanol WHSV was 100 h−1 based on the amount ofmolecular sieve in the reactor bed.

Example 1

[0154] One thousand grams of ZrOCl2.8H2O was dissolved with stirring in3.0 liters of distilled water. Another solution containing 400 grams ofconcentrated NH4OH and 3.0 liters of distilled water was prepared. Bothsolutions were heated to 60° C. These two heated solutions were combinedat a rate of 50ml/min using nozzle mixing. The pH of the final compositewas adjusted to approximately 9 by the addition of concentrated ammoniumhydroxide. This slurry was then put in polypropylene bottles and placedin a steambox (100° C.) for 72 hours. The product formed was recoveredby filtration, washed with excess water, and dried overnight at 85° C. Aportion of this product was calcined to 700° C. in flowing air for 3hours to produce an active zirconium oxide material.

Example 2

[0155] Five hundred grams of ZrOCl2.8H2O and 84 grams of La(NO3)3.6H2Owere dissolved with stirring in 3.0 liters of distilled water. Anothersolution containing 260 grams of concentrated NH4OH and 3.0 liters ofdistilled water was prepared. Both solutions were heated to 60° C. andthen combined at the rate of 50 ml/min using nozzle mixing to form thefinal mixture, a slurry. The pH of the final mixture was adjusted toapproximately 9 by the addition of concentrated ammonium hydroxide. Thisslurry was then put in a polypropylene bottle and placed in a steam box(100° C.) for 72 hours. The resulting product formed was recovered byfiltration, washed with excess water, and dried overnight at 85° C. Aportion of this product, was calcined to 700° C. in flowing air for 3hours to produce an active mixed metal oxide containing a nominal 10weight percent La (lanthanum) based on the final weight of the mixedmetal oxide.

Example 3

[0156] Fifty grams of ZrOCl2.8H2O were dissolved with stirring in 300 mlof distilled water. Another solution containing 4.2 grams ofLa(NO3)3.6H2O and 300 ml of distill water was prepared. These twosolutions were combined with stirring to form a final mixture. The pH ofthe final mixture, a slurry, was adjusted to approximately 9 by theaddition of concentrated ammonium hydroxide (28.9 grams). This slurrywas then put in a polypropylene bottle and placed in a steam box (100°C.) for 72 hours. The resulting product formed was recovered byfiltration, washed with excess water, and dried overnight at 85° C. Aportion of this resulting product was calcined to 700° C. in flowing airfor 3 hours to produce an active mixed metal oxide containing a nominal5 weight percent La based on the final weight of the mixed metal oxide.

Example 4

[0157] Five hundred grams of ZrOCl2.8H2O and 70 grams of Y(NO3)3.5H2Owere dissolved with stirring in 3.0 liters of distilled water. Anothersolution containing 260 grams of concentrated NH4OH and 3.0 liters ofdistilled water was prepared. Both solutions were heated to 60° C. andthen combined at the rate of 50 ml/min using nozzle mixing to form afinal mixture. The pH of the final mixture, a slurry, was adjusted toapproximately 9 by the addition of concentrated ammonium hydroxide. Thisslurry was then put in a polypropylene bottle and placed in a steam box(100° C.) for 72 hours. The resulting product formed was recovered byfiltration, washed with excess water, and dried overnight at 85° C. Aportion of the resulting product was calcined to 700° C. in flowing airfor 3 hours to produce an active mixed metal oxide containing a nominal10 weight percent Y (yttrium) based on the final weight of the mixedmetal oxide.

Example 5

[0158] Five hundred grams of ZrOCl2.8H2O and 56 grams of Ca(NO3)2.4H2Owere dissolved with stirring in 3000 ml of distilled water. Anothersolution containing 260 grams of NH4OH and 3000 ml of distilled waterwas prepared. These two solutions were combined with stirring. The pH ofthe final composite was adjusted to approximately 9 by the addition ofconcentrated ammonium hydroxide (160 grams). This slurry was then put inpolypropylene bottles and placed in a steambox (100° C.) for 72 hours.The resulting product formed was recovered by filtration, washed withexcess water, and dried overnight at 85° C. A portion of this productwas calcined to 700° C. in flowing air for 3 hours to produce an activemixed metal oxide containing a nominal 5 weight percent Ca (calcium)based on the final weight of the mixed metal oxide.

Example 6

[0159] Seventy grams of TiOSO₄·xH₂SO₄·xH₂O (x=1) were dissolved withstirring in 400 ml of distilled water. Another solution containing 12.8grams of CeSO₄ and 300 ml of distilled water was prepared. These twosolutions were combined with stirring. The pH of the final composite wasadjusted to approximately 8 by the addition of concentrated ammoniumhydroxide (64.3 grams). This slurry was then put in polypropylenebottles and placed in a steambox (100° C.) for 72 hours. The productformed was recovered by filtration, washed with excess water, and driedovernight at 85° C. A portion of this product was calcined to 700° C. inflowing air for 3 hours to produce an active mixed metal oxidecontaining a nominal 5 weight percent Ce based on the final weight ofthe mixed metal oxide.

Example 7

[0160] Five grams of HfOCl₂·xH₂O was dissolved with stirring in 100 mlof distilled water. The pH of the final composite was adjusted toapproximately 9 by the addition of concentrated ammonium hydroxide (4.5grams). This slurry was then put in a polypropylene bottle and placed ina steambox (100° C.) for 72 hours. The product formed was recovered byfiltration, washed with excess water, and dried overnight at 85° C. Aportion of this catalyst was calcined to 700° C. in flowing air for 3hours to produce an active hafnium oxide.

Example 8

[0161] Five grams of HfOCl₂·xH₂O and 0.62 grams of La(NO₃)₃·6H₂O weredissolved with stirring in 100 ml of distilled water. The pH of thefinal composite was adjusted to approximately 9 by the addition ofconcentrated ammonium hydroxide (3.5 grams). This slurry was then put ina polypropylene bottle and placed in a steambox (100° C.) for 72 hours.The product formed was recovered by filtration, washed with excesswater, and dried overnight at 85° C. A portion of this catalyst wascalcined to 700° C. in flowing air for 3 hours to produce an activemixed metal oxide containing a nominal 5 weight % La based on the finalweight of the mixed metal oxide.

Example 9

[0162] The carbon dioxide uptake of the oxides of Examples 1 through 8were measured using a Mettler TGA/SDTA 851 thermogravimetric analysissystem under ambient pressure. The metal oxide samples were firstdehydrated in flowing air to about 500° C. for one hour after which theuptake of carbon dioxide was measured at 100° C. The surface area of thesamples were measured in accordance with the method of Brunauer, Emmett,and Teller (BET) to provide the carbon dioxide uptake in terms of mgcarbon dioxide/m² of the metal oxide presented in Table 1. TABLE 1Catalyst Dry Surface Area CO₂ Uptake Example Weight (mg) mg of CO₂(m²/g) (mg of CO₂/m²) 1 76 0.0980 29 0.045 2 115 0.7781 80 0.085 3 730.4243 89 0.065 4 97 0.3808 100 0.039 5 78 0.5399 85 0.081 6 43 0.103550 0.048 7 158 0.3704 25 0.094 8 164 0.7359 60 0.075

Example 10 (Comparative)

[0163] The performance of the control, the molecular sieve of Example A,MSA, using a 50 mg load in the reactor and under the conditionsdiscussed above in Example B is reported in Tables 2 and 3.

Example 11

[0164] In this Example, the catalyst composition consisted of 40 mg MSAof Example A and 10 mg of the active zirconium oxide of Example 1. Thecatalyst composition and active mixed metal oxide were well mixed, andthen diluted with quartz to form the reactor bed. The results of testingthis catalyst composition in the process of Example B are shown inTables 2 and 3. The results indicate that the addition of the activezirconium oxide to the catalyst bed increased the lifetime of themolecular sieve composition significantly, and decreased the amounts ofundesired ethane and propane.

Example 12

[0165] In this Example, the catalyst composition consisted of 40 mg MSAof Example A and 10 mg of the active mixed metal oxide containing 10weight percent La, described in Example 2. The catalyst composition andactive mixed metal oxide were well mixed, and then diluted with quartzto form the reactor bed. The results of testing this catalystcomposition in the process of Example B are shown in Tables 2 and 3. Thedata in Tables 2 and 3 illustrate that by constituting 20% of thecatalyst composition load with the active mixed metal oxide containing10 weight percent La, the lifetime of the molecular sieve doubled, asindicated by its LEI value of 2. In addition, there was a net gain of1.7% in prime olefins on an absolute basis, with most of this gain beingdue to an increase in propylene of 2.76%, offsetting a small decrease inethylene of 1.07%. Selectivity to ethane decreased by 39% andselectivity to propane decreased by 37% suggesting that hydrogentransfer reactions have been significantly reduced.

Example 13

[0166] In this Example, the catalyst consisted of 30 mg MSA of Example Aand 20 mg of the active mixed metal oxide containing 10 weight percentLa, as described in Example 2. The catalyst composition and active mixedmetal oxide were well mixed, and then diluted with quartz to form thereactor bed. The results of testing this catalyst composition in theprocess of Example B are shown in Tables 2 and 3. The data of Tables 2and 3 illustrate that by constituting 40% of the catalyst compositionload containing 10 weight percent La, the lifetime of the SAPO-34catalyst composition increased by 440%. Trends in selectivity for thiscatalyst loading are similar to those seen in Example 8.

Example 14

[0167] In this Example, the catalyst composition consisted of 40 mg MSAfrom Example A and 10 mg of the active mixed metal oxide containing 10weight percent Y, as described in Example 4. The catalyst compositionand active mixed metal oxide were well mixed, and then diluted withquartz to form the reactor bed. The results of testing this catalystcomposition in the process of Example B are shown in Tables 2 and 3. Thesubstitution of yttrium for lanthanum has the effect of increasing theLEI even further. However, the improvements in selectivity are not asdramatic as seen with the lanthanum, with the gain in prime olefin being1.2% on an absolute basis.

Example 15

[0168] In this Example, the catalyst consisted of 40 mg MSA of Example Aand 10 mg of the active mixed metal oxide containing 5 weight percentLa, as described in Example 3. The catalyst composition and active mixedmetal oxide were well mixed, and then diluted with quartz to form thereactor bed. The results of testing this catalyst composition in theprocess of Example B are shown in Tables 2 and 3. It will be seen thatthe active mixed metal oxide containing 5 weight percent lanthanum oxideseems to have a much stronger effect in increasing the LEI than theactive mixed metal oxide of Example 8 containing 10 weight percent La.

Example 16

[0169] In this Example 16, the catalyst consisted of 40 mg MSA ofExample A and 10 mg of an active mixed metal oxide containing 5 weightpercent Ca, as described in Example 5. The catalyst composition andactive mixed metal oxide were well mixed, and then diluted with quartzto form the reactor bed. The results of this experiment in the reactorand conditions discussed above in Example B are shown in Tables 2 and 3.The active mixed metal oxide containing 5 weight percent calcium oxidehas increased the lifetime of the molecular sieve composition by 223%.

Example 17 (Comparative)

[0170] In this Comparative Example, the catalyst composition consistedof 40 mg MSA of Example A and 10 mg of an amorphous silica/alumina, aninactive mixed metal oxide. The molecular sieve catalyst composition andthe inactive mixed metal oxide catalysts were well mixed, and thendiluted with quartz to form the reactor bed. The results of testing thiscatalyst composition in the process of Example B are also shown inTables 2 and 3. This Comparative Example 17 illustrates a reduction inLEI to a value less than 1.0 when an inactive mixed metal oxide isutilized as compared to Example 11 of the invention. In addition, thereis a loss of 1.07% in prime olefin selectivity, and no significantreduction in ethane and propane production.

Example 18

[0171] In this Example, the catalyst composition consisted of 40 mg MSAfrom Example A and 10 mg an active mixed metal oxide containing Ce andtitania, as described in Example 6. The catalyst composition and activemixed metal oxide were well mixed, and then diluted with quartz to formthe reactor bed. The results of testing this catalyst composition in theprocess of Example B are shown in Tables 2 and 3. The presence of theactive mixed metal oxide increased the lifetime of the molecular sievecomposition by 134%.

Example 19

[0172] In this Example, the catalyst composition consisted of 40 mg MSAof Example A and 10 mg of the active hafnium metal oxide described inExample 7. The catalyst composition and active metal oxide were wellmixed, and then diluted with quartz to form the reactor bed. The resultsof testing this catalyst composition in the process of Example B areshown in Tables 2 and 3. The data in Tables 2 and 3 illustrate that byconstituting 20% of the catalyst composition load with the activehafnium metal oxide, the lifetime of the molecular sieve has increasedby 126%. Selectivity to ethane decreased by 40% and selectivity topropane decreased by 46% suggesting that hydrogen transfer reactionshave been significantly reduced.

Example 20

[0173] In this Example, the catalyst composition consisted of 40 mg MSAof Example A and 10 mg of the active mixed metal oxide containing 5weight percent La, described in Example 8. The catalyst composition andactive mixed metal oxide were well mixed, and then diluted with quartzto form the reactor bed. The results of testing this catalystcomposition in the process of Example B are shown in Tables 2 and 3. Thedata in Tables 2 and 3 illustrate that by constituting 20% of thecatalyst composition load with the active mixed metal oxide containing 5weight percent La, the lifetime of the molecular sieve has increased by150%. Selectivity to ethane decreased by 51% and selectivity to propanedecreased by 51% suggesting that hydrogen transfer reactions have beensignificantly reduced. TABLE 2 Reactor Bed Prime C₃ Exam- CompositionOlefin C₂=/ Purity ple (wt%) LEI (%) C₃= (%) 10 100% MSA 1 74.65 0.9292.7 (Comp) 11 80% MSA / 2.64 74.79 0.82 96.1 20% ZrO₂ 12 80% MSA / 2.0376.34 0.84 95.6 20% of 10% La/ZrO₂ 13 60% MSA / 5.41 75.50 0.85 94.6 40%of 10% La/ZrO₂ 14 80% MSA / 2.79 75.81 0.85 94.9 20% of 10% Y/ZrO₂ 1580% MSA / 4.85 75.84 0.84 94.8 20% of 5% La/ZrO₂ 16 80% MSA / 3.23 73.850.79 96.7 20% of 5% Ca/ZrO₂ 17 80% MSA / (Comp) 20% of SiO₂/ Al₂O₃ 1880% MSA / 2.34 65.65 0.87 95.1 20% of Ce/ TiO₂ 19 80% MSA / 2.26 72.980.71 96.2 20% of HfO₂ 20 80% MSA / 2.50 72.75 0.76 96.5 20% of 5%La/HfO₂

[0174] TABLE 3 Product Selectivities (%) Exam- Reactor ple Bed (wt %)CH₄ C₂ ⁼ C₂ ^(o) C₃ ⁼ C₃ ^(o) C₄'s C₅+ 10 100% MSA 1.51 35.82 0.95 38.833.05 14.50 2.12 (Comp) 11 80% MSA / 1.50 33.74 0.53 41.05 1.68 14.793.31 20% ZrO₂ 12 80% MSA / 1.31 34.75 0.58 41.59 1.93 14.96 2.46 20% of10% La/ZrO₂ 13 60% MSA / 1.47 34.75 0.66 40.75 2.32 14.76 2.52 40% of10% La/ZrO₂ 14 80% MSA / 1.32 34.92 0.66 40.88 2.20 14.41 3.07 20% of10% Y/ZrO₂ 15 80% MSA / 1.26 34.59 0.64 41.25 2.28 14.96 2.52 20% of 5%La/ZrO₂ 16 80% MSA / 1.50 32.65 0.42 41.20 1.43 14.84 5.34 20% of 5%Ca/ZrO₂ 17 80% MSA / 2.17 35.46 0.89 38.12 2.72 14.21 2.65 (Comp) 20% ofSiO₂/Al₂O₃ 18 80% MSA / 6.79 30.57 0.75 35.09 1.80 12.72 3.97 20% of Ce/TiO₂ 19 80% MSA / 1.98 31.62 0.52 41.36 1.65 14.64 4.93 20% of HfO₂ 2080% MSA / 1.98 31.58 0.47 41.18 1.49 14.53 5.52 20% of 5% La/HfO₂

[0175] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that themolecular sieve compositions described herein are useful as absorbents,adsorbents, gas separators, detergents, water purifiers, and for othervarious uses such as agriculture and horticulture. It is within thescope of this invention to add one or more active metal oxide(s) to thesynthesis mixture for making a molecular sieve as described above. Forthis reason, then, reference should be made solely to the appendedclaims for purposes of determining the true scope of the presentinvention.

We claim:
 1. A catalyst composition comprising a molecular sieve and atleast one oxide of a metal selected from Group 4 of the Periodic Tableof Elements, wherein said metal oxide has an uptake of carbon dioxide at100° C. of at least 0.03 mg/m² of the metal oxide.
 2. The catalystcomposition of claim 1 wherein said metal oxide has an uptake of carbondioxide at 100° C. of at least 0.035 mg/m² of the metal oxide.
 3. Thecatalyst composition of claim 1 wherein said metal oxide has an uptakeof carbon dioxide at 100° C. of less than 10 mg/m² of the metal oxide.4. The catalyst composition of claim 1 wherein said metal oxide has anuptake of carbon dioxide at 100° C. of less than 5 mg/m² of the metaloxide.
 5. The catalyst composition of claim 1 and also including atleast one of a binder and a matrix material different from said metaloxide.
 6. The catalyst composition of claim 1 wherein said metal oxidehas a surface area greater than 10 m²/g.
 7. The catalyst composition ofclaim 1 and also including a binder and a matrix material each beingdifferent from one another and from said metal oxide.
 8. The catalystcomposition of claim 7 wherein the binder is an alumina sol and thematrix material is a clay.
 9. The catalyst composition of claim 1wherein said metal oxide is selected from zirconium oxide and hafniumoxide.
 10. The catalyst composition of claim 1 and also including anoxide of a metal selected from Group 2 and Group 3 of the Periodic Tableof Elements. 11 The catalyst composition of claim 10 wherein the Group 4metal oxide comprises zirconium oxide and the Group 2 and/or Group 3metal oxide comprises one or more oxides selected calcium oxide, bariumoxide, lanthanum oxide, yttrium oxide and scandium oxide.
 12. Thecatalyst composition of claim 1 wherein the molecular sieve comprises aframework including at least two tetrahedral units selected from [SiO₄],[AlO₄] and [PO₄] units.
 13. The catalyst composition of claim 12 whereinthe molecular sieve comprises a silicoaluminophosphate.
 14. The catalystcomposition of claim 12 wherein the molecular sieve comprises a CHAframework-type molecular sieve.
 15. The catalyst composition of claim 14wherein the molecular sieve further comprises an AEI framework-typemolecular sieve.
 16. The catalyst composition of claim 1 wherein theweight ratio of the molecular sieve to metal oxide is in the range offrom 5 percent to 800 percent.
 17. A molecular sieve catalystcomposition comprising an active Group 4 metal oxide and a Group 2and/or a Group 3 metal oxide, a binder, a matrix material, and asilicoaluminophosphate molecular sieve.
 18. A method for making acatalyst composition, the method comprising physically mixing firstparticles comprising a molecular sieve with second particles comprisinga Group 4 metal oxide having an uptake of carbon dioxide at 100° C. ofat least 0.03 mg/m² of the metal oxide particles.
 19. The method ofclaim 18 wherein said second particles have a surface area greater than10 m²/g.
 20. The method of claim 18 wherein said second particles have asurface area greater than 15 m²/g.
 21. The method of claim 18 whereinsaid first particles comprise a silicoaluminophosphate molecular sieveand/or an aluminophosphate molecular sieve.
 22. The method of claim 18wherein at least one said first and said second particles also includeat least one of a binder and a matrix material.
 23. The method of claim18 wherein said first particles comprise a silicoaluminophosphatemolecular sieve, a binder including an alumina sol and a matrix materialincluding a clay.
 24. The method of claim 18 wherein said secondparticles also comprise a Group 2 and/or Group 3 metal oxide.
 25. Themethod of claim 18 wherein said second particles comprise zirconiumoxide and at least one of calcium oxide, barium oxide, lanthanum oxide,yttrium oxide and scandium oxide.
 26. A method of making a catalystcomposition, the method comprising: (i) synthesizing a molecular sievefrom a reaction mixture comprising at least one templating agent and atleast two of a silicon source, a phosphorus source and an aluminumsource; and (ii) recovering the molecular sieve synthesized in (i);(iii) forming a hydrated precursor of a Group 4 metal oxide byprecipitation from a solution containing a source of Group 4 metal ions;(iv) recovering the hydrated precursor formed in (iii); (v) calciningthe hydrated precursor recovered (iv) to form a calcined Group 4 metaloxide that has an uptake of carbon dioxide at 100° C. of at least 0.03mg/m² of the metal oxide; and (vi) physically mixing the molecular sieverecovered in (i) and the calcined metal oxide produced in (v).
 27. Themethod of claim 26 wherein the molecular sieve and/or the Group 4 metaloxide is combined with a binder and/or a matrix material prior to (vi).28. The method of claim 26 wherein the weight ratio of the molecularsieve to the calcined metal oxide is in the range of from 30 percent to400 percent.
 29. The method of claim 26 wherein the calcined metal oxidehas a surface area greater than 10 m²/g.
 30. The method of claim 26wherein the molecular sieve is spray dried with a matrix material and abinder prior to (vi).
 31. The method of claim 30 wherein the molecularsieve is a silicoaluminophosphate, the binder is an alumina sol and thematrix material is a clay.
 32. The method of claim 26 wherein a mixedmetal oxide is produced in (iii) by precipitation from at least onesolution containing a Group 4 metal oxide precursor and at least one ofa Group 2 metal oxide precursor and a Group 3 metal oxide precursor. 33.The method of claim 26 wherein said precipitation is conducted at a pHabove
 7. 34. The method of claim 26 wherein (iii) also includeshydrothermally treating the precipitate at a temperature of at least 80°C. for up to 10 days.
 35. The method of claim 26 wherein (v) isconducted at a temperature in the range of from about 400° C. to about900° C.
 36. A process for converting a feedstock into one or moreolefin(s) in the presence of a catalyst composition comprising amolecular sieve and an active Group 4 metal oxide having an uptake ofcarbon dioxide at 100° C. of at least 0.03 mg/m² of the metal oxide. 37.The process of claim 36 wherein said metal oxide has an uptake of carbondioxide at 100° C. of at least 0.035 mg/m² of the metal oxide.
 38. Theprocess of claim 36 wherein said metal oxide has an uptake of carbondioxide at 100° C. of less than 10 mg/m² of the metal oxide.
 39. Theprocess of claim 36 wherein said metal oxide has an uptake of carbondioxide at 100° C. of less than 5 mg/M² of the metal oxide.
 40. Theprocess of claim 37 and also including at least one of a binder and amatrix material different from said metal oxide.
 41. The process ofclaim 37 and also including a binder and a matrix material each beingdifferent from one another and from said metal oxide.
 42. The process ofclaim 41 wherein the binder is an alumina sol.
 43. The process of claim41 wherein the matrix is a clay.
 44. The process of claim 36 wherein thecatalyst composition has a Lifetime Enhancement Index (LEI) greaterthan
 1. 45. The process of claim 36 wherein the molecular sieve issynthesized from reaction mixture comprising at least two of a siliconsource, a phosphorus source and an aluminum source, optionally in thepresence of a templating agent.
 46. The process of claim 36 wherein themolecular sieve is a silicoaluminophosphate.
 47. The process of claim 36wherein the catalyst composition also includes an active Group 2 and/orGroup 3 metal oxide.
 48. The process of claim 36 wherein the feedstockcomprises methanol and/or dimethylether.
 49. A process for converting afeedstock into one or more olefin(s) in the presence of a molecularsieve catalyst composition comprising a molecular sieve, a binder, amatrix material and a mixture of metal oxides different from the binderand the matrix material.
 50. The process of claim 49 wherein the mixtureof metal oxides comprises a Group 4 metal oxide in combination with aGroup 2 and/or Group 3 metal oxide.
 51. A process for convertingfeedstock into one or more olefin(s) in the presence of the catalystcomposition prepared by the method of claim
 18. 52. A process forconverting feedstock into one or more olefin(s) in the presence of thecatalyst composition prepared by the method of claim
 26. 53. A processfor producing one or more olefin(s), the process comprising: (a)introducing a feedstock comprising at least one oxygenate to a reactorsystem in the presence of a catalyst composition comprising a molecularsieve, a binder, a matrix material, and an active Group 4 metal oxide;(b) withdrawing from the reactor system an effluent stream containingone or more olefins; and (c) passing the effluent stream through arecovery system; and (d) recovering at least the one or more olefin(s).54. The process of claim 53 wherein the binder is an alumina sol. 55.The process of claim 53 wherein the matrix material is a clay.
 56. Theprocess of claim 53 wherein the molecular sieve is asilicoaluminophosphate molecular sieve and/or an aluminophosphatemolecular sieve.
 57. The process of claim 53 wherein the active Group 4metal oxide is an active zirconium metal oxide or an active hafniummetal oxide or a mixture thereof.
 58. The process of claim 53 whereinthe active Group 4 metal oxide has an uptake of carbon dioxide at 100°C. of at least 0.03 mg/m² of the metal oxide.
 59. The process of claim53 wherein the catalyst composition also includes an active Group 2and/or Group 3 metal oxide.
 60. The process of claim 53 wherein thefeedstock comprises methanol and/or dimethylether.
 61. The process ofclaim 53 wherein the active metal oxide has a surface area greater than10 m²/g.
 62. The process of claim 53 wherein the LEI of the catalystcomposition is greater than that for the same catalyst compositionwithout the active metal oxide.
 63. The process of claim 53 wherein thesieve catalyst composition has an LEI greater than 1.5.
 64. Anintegrated process for making one or more olefin(s), the integratedprocess comprising: (a) passing a hydrocarbon feedstock to a syngasproduction zone to produce a synthesis gas stream; (b) contacting thesynthesis gas stream with a catalyst to form an oxygenated feedstock;and (c) converting the oxygenated feedstock into the one or moreolefin(s) in the presence of a molecular sieve catalyst compositioncomprising a molecular sieve and an active metal oxide.
 65. Theintegrated process of claim 64 wherein the process further comprises (d)polymerizing the one or more olefin(s) in the presence of apolymerization catalyst into a polyolefin.
 66. The integrated process ofclaim 64 wherein the oxygenated feedstock comprises methanol, theolefin(s) include ethylene and propylene, and the active metal oxide isan active Group 4 metal oxide having a surface area greater than 10m²/g.
 67. The integrated process of claim 66 wherein the Group 4 metaloxide is an active zirconium oxide.
 68. The integrated process of claim66 wherein the molecular sieve is a silicoaluminophosphate molecularsieve.